Springer Series in

Surface Sciences
Editor: Robert Gomer 25

Springer-Verlag Berlin Heidelberg GmbH

Springer Series in Surface Sciences
Editors: G. Ertl, R. Gomer and D. L. Mills Managing Editor: H.K.V. Latsch

Physisorption Kinetics 20 Scanning Tunneling Microscopy I

By H. J. Kreuzer. Z. W. Gortel General Principles and Applications to Clean
2 The Structure of Surfaces and Adsorbate-Covered Surfaces
Editors: M. A. Van Hove, S. Y. Tong Editors: H.-J. Gtintherodt, R. Wiesendanger
2nd Edition
3 Dynamical Phenomena at Surfaces, Interfaces
and Superlattices 21 Surface Phonons
Editors: F. Nizzoli, K.-H. Rieder, R. F. Willis Editors: W. Kress, F. W. de Wette

4 Desorption Induced by Electronic Transitions, 22 Chemistry and Physics of Solid Surfaces VIII
DIET II Editors: R. Vanselow, R. Howe
Editors: W. Brenig, D. Menzel 23 Surface Analysis Methods in Materials
5 Chemistry and Physics of Solid Surfaces VI Science
Editors: R. Vanselow, R. Howe Editors: D. J. O'Connor, B. A. Sexton,
R. SI. C. Smart
6 Low-Energy Electron Diffraction
Experiment, Theory 24 The Structure of Surfaces III
and Surface Stmcture Determination Editors: S. Y. Tong, M. A. Van Hove,
By M. A. Van Hove, W. H. Weinberg, C.-M. Chan K. Takayanagi, X. D. Xie

7 Electronic Phenomena in Adsorption 25 NEXAFS Spectroscopy

and Catalysis By J. StOhr
By V. F. Kiselev, O. V. Krylov 26 Semiconductor Surfaces and Interfaces
8 Kinetics ofinterface Reactions ByW. Monch
Editors: M. Gmnze, H. J. Kreuzer 2nd Edition

9 Adsorption and Catalysis on Transition Metals 27 Helium Atom Scattering from Surfaces
and Their Oxides Editor: E. Hulpke
By V. F. Kiselev, O. V. Krylov 28 Scanning Tunneling Microscopy II
10 Chemistry and Physics of Solid Surfaces VII Further Applications
Editors: R. Vanselow. R. Howe and Related Scanning Techniques
Editors: R. Wiesendanger, H.-J. Giintherodt
II The Structure of Surfaces II 2nd Edition
Editors: J. F. van der Veen, M. A. Van Hove
29 Scanning Tunneling Microscopy III
12 Diffusion at Interfaces: Microscopic Concepts Theory of STM
Editors: M. Gmnze, H. J. Kreuzer, J. J. Weimer and Related Scanning Probe Methods
13 Desorption Induced by Electronic Transitions, Editors: R. Wiesendanger, H.-J. Gtintherodt
DIET III 2nd Edition
Editors: R. H. Stulen, M. L. Knotek 30 Concepts in Surface Physics
14 Solvay Conference on Surface Science By M. C. Desjonqueres, D. Spanjaard*)
Editor: F. W. de Wette 31 Desorption Induced by Electronic Transitions,
15 Surfaces and Interfaces of Solids DIET V
By H. Ltith*) Editors: A. R. Burns, E. B. Stechel,
16 Atomic and Electronic Structure of Surfaces D. R. Jennison
Theoretical Foundations 32 Scanning Tunneling Microscopy
By M. Lannoo, P. Friedel and its Application
17 Adhesion and Friction By C. Bai
Editors: M. Gmnze, H. J. Kreuzer 33 Adsorption on Ordered Surfaces
18 Auger Spectroscopy and Electronic Structure of Ionic Solids and Thin Films
Editors: G. Cubiotti, G. Mondio, K. Wandelt Editors: H.-J. Freund, E. Umbach

19 Desorption Induced by Electronic Transitions, 34 Surface Reactions

Editor: R. J. Madix
DIET IV
Editors: G. Betz, P. Varga 35 Applications of Synchrotron Radiation
High-Resolution Studies of Molecules
and Molecular Adsorbates on Surfaces
*) Available as a textbook Editor: W. Eberhardt
Joachim Stohr

NEXAFS
Spectroscopy

With 177 Figures

Dr. Joachim StOhr
IBM Almaden Research Center, 650 Harry Road,
San Jose, CA 95120-6099, USA

Series Editors
Professor Dr. Gerhard Ertl
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6,
D-14195 Berlin, Germany

Professor Robert Gomer, Ph.D.

The James Franck Institute, The University of Chicago, 5640 Ellis Avenue,
Chicago, IL 60637, USA

Professor Douglas L. Mills, Ph.D.

Department of Physics, University of California,
Irvine, CA 92717, USA

Managing Editor: Dr.-Ing. Helmut K. V. Lotsch

Springer-Verlag, TIergartenstrasse 17,
D-69121 Heidelberg, Germany

First Edition 1992

Corrected Printing 1996
ISBN 978-3-642-08113-2 ISBN 978-3-662-02853-7 (eBook)
DOI 10.1007/978-3-662-02853-7

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Die Deutsche Bibliothek - CIP-Einheitsaufnahme.
StOhr, Joachim: NEXAFS spectroscopy 1 Joachim StOhr. - Corr. 2. printing. -
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Santa Clara; Singapore; Tokyo : Springer, 1996
(Springer series in surface sciences; 25)
ISBN 978-3-642-08113-2
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 To Megan
All too often the thought of you had to substitute for your presence.
Yet, what a lucky man I am to have a daughter with so much life!
Preface

The purpose of this book is the development of the principles and experimental
techniques underlying near edge X-ray absorption fine structure (NEXAFS)
spectroscopy and the demonstration of the power of the technique for the study
of the electronic and crystallographic structure of low-Z molecules bonded to
surfaces. Low-Z molecules are defined as those consisting of hydrogen, carbon,
nitrogen, oxygen and/or fluorine atoms, which are particularly important in
surface chemistry. This book is the first comprehensive treatment of the subject
and presents a unified picture of theoretical and experimental concepts and
results. It develops all concepts from an elementary level and is suitable for
students and researchers without extensive prior knowledge in X-ray absorption
spectroscopy. On the other hand, it discusses state-of-the-art instrumentation,
analysis techniques, and experimental and theoretical results and is therefore
also suited for the advanced spectroscopist. The spectra of free molecules are
discussed first, since their understanding provides the basis for understanding
spectra of molecules bonded to surfaces, the main topic of the book. The
connection to spectra of polymeric molecules is also made. The book may
therefore be of interest not only to surface scientists but also to researchers
studying free molecules or polymers. The various molecular adsorption systems
studied by NEXAFS are tabulated. Future scientific opportunities making use
of the NEXAFS technique in conjunction with advanced synchrotron radiation
sources are also discussed. These range from element-specific microscopy stud-
ies of solid surfaces to studies of molecular conformations at liquid surfaces.

Portola Valley, CA J. Stohr

January 1991
Acknowledgements

I started writing this book in November 1987 and thought I could finish it in a year. Little
did I know ... , most notably, that I knew too little. If nothing else, it's been worthwhile
writing this book for all that I have learned!
The Stanford Synchrotron Radiation Laboratory (SSRL) has played a crucial role in
my own research and in the development of NEXAFS spectroscopy. I have fond
memories of the excitement that hovered in the air in the early years of the Laboratory
and I consider myself lucky to have been a part of it. I also remember the frustrations
associated with doing synchrotron radiation research ... the endless hours of waiting for
the beam. It certainly has been a love-hate relationship (more love)! It is only fitting to
start the acknowledgements by thanking the SSRL staff who made the Laboratory hum.
Artie Bienenstock deserves a special word ofthanks because he made it possible for me to
start my own research program during my years on the SSRL staff (1977-1981)-rumor
has it, at the expense of some outside users.
Over the last ten years I have benefited from the help of many people, and I need to
mention a few. It was Dave Shirley who first threw the idea at me in 1976 to do
Absorption Spectroscopy for Chemical Analysis (ASCA). Except for a few measurements
on polymer films the idea did not go far in my postdoc days at Lawrenae Berkeley
Laboratory. It did, however, stimulate my interest in X-ray absorption spectroscopy and
later led to my involvement with SEXAFS and NEXAFS. Rolf Jaeger was the key person
who did the first NEXAFS experiments with me in 1980. What an exciting time and what
great collaboration it was!
In my EXXON years, 1981-1985, I met the late Earl Muetterties who taught me that
in chemistry there are other molecules besides CO, and so his student Allen Johnson and
I began the study of organic molecules. I remember Allen drawing structural formulas for
me at SSRL and teaching me about molecules like cyciooctatetraene that I had never
heard of. I also learned more chemistry and surface chemistry through interactions with
John Horsley and John Gland. John Horsley deepened my understanding ofthe K-shell
spectra of molecules. John Gland taught me about desulfurization and other catalytic
reactions of molecules with surfaces. During 1983/84 I had the pleasure of working with
Francesco Sette for a memorable year. We both lived near Brookhaven National
Laboratory to do experiments at the National Synchrotron Light Source but ironically
had to fly to California to see the light (at SSRL). Our brainstorming sessions about the
spectra were great fun, and Francesco often awed me with his scientific knowledge. The
lack of photons at Brookhaven also had its good side, it left me enough spare time to
learn how to windsurf on the Long Island Sound. During this time I also started to
collaborate with Adam Hitchcock, a collaboration that has continued to this day. After
reading this book it will be easy for the reader to judge the depth of this collaboration.
Adam has not only been a great source of information for me but he always shared his
knowledge and unpublished data in a truly scientific spirit.
After "coming home" to California and starting work at IBM in 1985 I had the
pleasure of ciosely working with Duane Outka. Duane was so independent and efficient
that I could have spent my winters skiing at Lake Tahoe. Instead, I only went skiing
occasionally and wrote a lot of papers with Duane. At this point I need to mention the
X Acknowledgements

special collaboration I have enjoyed since about 1982 with Bob Madix. It has involved
many students, of whom Duane, Paul Stevens and Jeff Solomon became true "syn-
chrotronjocks". My collaboration with Bob has been so successful because our interests,
at least initially, were quite complementary. He was after specific problems in surface
chemistry and my main goal was the development of new synchrotron techniques. I know
that at least I succeeded in learning and benefiting a great deal from him. The same is true
for my more recent collaboration with Cindy Friend. She and her students Jeff Roberts
and Albert Liu played a big role in teaching me the surface chemistry of organic
molecules.
When I realized that I didn't understand enough theory to write this book (I still may
not), I asked John Horsley, who in the meantime had also moved to Silicon Valley, to
give me his XIX multiple scattering code. John shared his programs without hesitation and
I am deeply indebted to him not only for his programs but for his constant advice and
teaching, all the way to critically reading some of the chapters of this book. The XIX
calculations were carried out by Wilfried Wurth, who, like previously Rolf Jaeger, had
been a student of Dietrich Menzel. As such he knew his science. I was fortunate that
Wilfried allowed me to look over his shoulder and he taught me while cranking out the
spectra of a large number of molecules. Alex Bradshaw deserves a "thank you" for
arguing with me and in the end teaching me about symmetry selection rules in NEXAFS.
A special word of thanks is due to my long time collaborator and friend Klaus
Baberschke, who as a visitor took part in the first NEXAFS experiment in 1980, and in
the meantime has established his own highly successful program in X-ray absorption
spectroscopy. Klaus and I have had our share offriendly arguments and discussions over
the years and I have learned a great deal from him, his students, and associates, especially
Dimitri Arvanitis. When beam time was scarce or non-available at SSRL he allowed me
to collaborate with him at BESSY. Some of these were the easiest experiments I ever
did - on the telephone.
I also need to express some thoughts about the IBM Almaden Research Center
where, besides my own home, this book was written. The laboratory is not only located in
beautiful surroundings, but it is a great place to do science. The following anecdote shows
why I have loved working there. I had been trying to dose benzoic acid onto the Ag(11O)
surface at SSRL but, because of its low vapor pressure (it is a solid), I had been
unsuccessful in dosing it without contamination. At IBM I mentioned my frustrations to
my boss George Castro, who advised me to sublime it a few times to clean it up. An hour
later he came by my office with a glass flask and said "Here, I sublimed some for you."
George also shared my vision about the importance of synchrotron radiation research
and he made the difference where it counts - getting the money to do it! At Almaden I
learned about polymers from Tom Russell and Jerry Swalen, and I greatly benefited from
stimulating discussions with the numerous surface scientists at the lab. Some noteworthy
conversations that left me truly breathless took place while running through the hills with
Dick Brundle, Hugh Brown and Charlie Rettner. During one of those runs, after I had
just become a manager and did not think that I could finish this book without a
coauthor, Charlie told me how much more respect he had for authors who did it on their
own. That decided it - how could I disappoint Charlie? The task of finishing this book
was greatly aided by my secretary Toni Vanderwege, who in many ways ran the
Department for me and gave me time to think and write.
Finally, a word of thanks and appreciation to Renee, who supported me in the
endeavor (or should I say ordeal) of writing this book. When my motivation dropped
toward the end she encouraged me not to succumb to this all-too-human tendency. It's
certainly harder to finish than to start, but what a feeling it is to be done!
Contents

1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Why Another Spectroscopy and Another Book? . . . . . . . . 1
1.2 Development of the NEXAFS Technique . . . . . . . . . . . . 4

2. Theory of Inner Shell Excitation Spectra . . . . . . . . . . . . 8

2.1 Description of the X-Ray Absorption Process. . . . . . 8
2.1.1 The X-Ray Absorption Cross Section . . . . . . 8
2.1.2 Optical Oscillator Strength and Sum Rules . . . . . .. 11
2.2 Time Scales in Inner-Shell Excitations . . . . . . . . . . . . .. 13
2.2.1 Electron and Hole Lifetimes . . . . . . . . . . . . . . . . 13
2.2.2 Separation of Electronic and Nuclear Degrees
of Freedom. . . . . . . . . . . . . . . . . . . . . . . . .. 14
2.3 The Electronic Ground State. . . . . . . . . . . . . . . . . . . . 15
2.3.1 The Hartree-Fock Method. . . . . . . . . . . . . . . . . 15
2.3.2 Roothaan-Hall and Semiempirical Methods. . . . . . . 19
2.4 Transition Energies . . . . . . . . . . . . . . . . . . . . . . . .. 20
2.4.1 Koopmans'Theorem.................... 21
2.4.2 The Transition State Method . . . . . . . . . . . . . .. 23
2.4.3 Localized Versus Delocalized Core Hole. . . . . . . .. 26
2.5 Transition Intensities . . . . . . . . . . . . . . . . . . . . . . .. 26
2.5.1 One-Electron Versus Multi-Electron Transitions. . .. 27
2.5.2 Effects of Nuclear Vibrations . . . . . . . . . . . . . .. 27
2.5.3 The Sudden Approximation . . . . . . . . . . . . . . .. 28
2.5.4 Adiabatic Versus Sudden Excitation . . . . . . . . . .. 29
2.6 Bound Versus Continuum Final States. . . . . . . . . . . . .. 30
2.6.1 Improved Virtual Orbitals . . . . . . . . . . . . . . . .. 30
2.6.2 Continuum Final States . . . . . . . . . . . . . . . . .. 31
2.7 The Xa Multiple Scattering Method. . . . . . . . . . . . . .. 34
2.7.1 Introduction to the Method. . . . . . . . . . . . . . .. 34
2.7.2 Exchange Potential and Latter Tail. . . . . . . . . . .. 34
2.7.3 Muffin Tin Potential . . . . . . . . . . . . . . . . . . .. 35
2.7.4 Multiple Scattering Wavefunctions . . . . . . . . . . .. 36
2.7.5 Transition Energies. . . . . . . . . . . . . . . . . . . .. 37
2.7.6 Practical Procedures for Calculation
of K-Shell Spectra. . . . . . . . . . . . . . . . . . . . .. 38
XII Contents

2.8 Ab Initio Stieltjes-Tchebycheff Molecular Orbital Method.. 39

2.8.1 Introduction to the Method. . . . . . . . . . . . . . .. 39
2.8.2 Calculational Procedure . . . . . . . . . . . . . . . . .. 39
2.8.3 Stieltjes-Tchebycheff Orbitals . . . . . . . . . . . . . .. 41
2.8.4 Feshbach-Fano Method . . . . . . . . . . . . . . . . .. 42
2.9 Shell-by-Shell Multiple Scattering Method. . . . . . . . . . .. 43
2.10 Approximations Leading to the EXAFS Equation. . . . . .. 44

3. Symmetry and Molecular Orbitals. . . . . . . . . . . . . . . . . . . 48

3.1 Origin and Labelling of Molecular Orbitals. . . . . . . . . . 48
3.2 Some Molecular Orbitals and Irreducible Representations . 49
3.2.1 Diatomics and Linear Triatomics. . . . . . . . . . . .. 49
3.2.2 Hydrogen Fluoride, Water, Ammonia, and Methane. 53
3.3 Molecular Orbitals, Equivalent Orbitals and Hybrid Orbitals 55
3.3.1 Molecular Orbital Versus Valence Bond Theory. . 55
3.3.2 Ionization Potentials in Methane . . . . . . . . . . . .. 58
3.3.3 Bonding in Ethane, Ethylene, and Acetylene . . . . .. 59
3.4 Interactions Between Localized Orbitals: Conjugation. . . .. 61
3.4.1 First and Second Order Perturbation Treatment. . .. 62
3.4.2 Interactions in Chain-Like Hydrocarbons. . . . . . .. 64
3.5 Splitting of Antibonding Orbitals
Due to Bond-Bond Interactions . . . . . . . . . . . . . . . . . 67
3.5.1 The Linear Combination of Bond Orbitals Method.. 67
3.5.2 Application to (J and n Bonds in Hydrocarbons . . .. 67
3.6 Orbital Orientation, Symmetry, and the Dipole Selection Rule 69
3.6.1 Orbital Orientation and Angular Dependence
of the Dipole Matrix Element . . . . . . . . . . . . . .. 69
3.6.2 Group Theory and the Dipole Selection Rule . . . . . 72
3.6.3 Applications of Group Theoretical Selection Rules .. 73
3.7 Spin-Dependent Excitations . . . . . . . . . . . . . . . 75

4. Experimental and Calculated K-Shell Spectra

of Simple Free Molecules . . . . . . . . . . . . . . .. . . . . . . . . .. 79
4.1 Experimental Methods: The ISEELS Techniques . . . . . . . 79
4.2 Characteristic Resonances in K-Shell Spectra. . . . 83
4.2.1 Overview........................... 83
4.2.2 n* Resonances . . . . . . . . . . . . . . . . . . . . . . .. 88
4.2.3 Rydberg and Mixed Valence/Rydberg Resonances. .. 90
4.2.4 (J* Shape Resonances. . . . . . . . . . . . . . . . . . .. 93
4.2.5 Multi-Electron Features . . . . . . . . . . . . . . . . .. 95
4.2.6 Correlation of Multiple Scattering and Molecular
Orbital Calculations: The N2 Molecule . . . . . . . .. 97
4.2.7 Molecular Orbitals and Resonances
of Simple Hydrocarbons. . . . . . . . . . . . . . . . .. 102
4.2.8 Exchange Splitting in the Oxygen Molecule. 104
4.3 Systematics of Resonance Positions . . . . . . . . . . . . . . . 106
 Contents XIII

5. Principles, Techniques, and Instrumentation of NEXAFS . . . . .. 114

5.1 Achieving Adsorbate Sensitivity. . . . . . . . . . . . 114
5.2 Electron Yield Detection. . . . . . . . . . . . . . . . 118
5.2.1 Principles..................... 118
5.2.2 Quantitative Description of Electron Yield . . . . . 122
5.2.3 Adsorbate Versus Substrate Signal . . . . . . . . . . .. 127
5.2.4 Experimental Details and Detectors . . . . . . . . . .. 130
5.3 Fluorescence Yield Detection . . . . . . . . . . . . . . . . . .. 133
5.3.1 Absorption and Scattering of Soft X-Rays. . . . . . .. 133
5.3.2 X-Ray Reflection and Diffuse Scattering. . . . . . . .. 137
5.3.3 Adsorbate Fluorescent Signal and Substrate Background 139
5.3.4 Practical Scheme for Suppression of Background Signal 141
5.3.5 Experimental Details and Detectors . . . . . . . . . .. 145
5.4 Comparison of Detection Techniques. . . . . . . . . . . . . .. 149
5.5 Normalization and Background Corrections . . . . . . . . .. 154
5.5.1 General Considerations. . . . . . . . . . . . . . . . . .. 154
5.5.2 Normalization by a Reference Monitor . . . . . . . .. 156
5.5.3 Division by the Clean Sample Spectrum. . . . . . . . 158
5.5.4 Subtraction of the Clean Sample Spectrum. . . . . . 160
6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules:
An Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
6.1 From Free to Chemisorbed Molecules. . . . . . . . . . . . 162
6.1.1 Influence of Extra-Molecular Interactions
on K-Shell Spectra . . . . . . . . . . . . . . . . . . . 162
6.1.2 X-Ray Polarization and Molecular Orientation 169
6.2 Chemisorbed Atoms Versus Molecules. . . . . . . . . . . . .. 172
6.2.1 The NEXAFS Region. . . . . . . . . . . . . . . . . . .. 172
6.2.2 The SEXAFS Region . . . . . . . . . . . . . . . . . . 176
6.3 The Building Block Approach for Large Molecules 179
6.3.1 Assembly of Pseudodiatomics . . . . . . . . . . . . . 179
6.3.2 Experimental Examples: Free, Adsorbed,
and Polymeric Molecules . . . . . . . . . . . . . . . . . 179
6.3.3 Theoretical Foundation of the Building Block Picture 183
6.4 Limitations of the Building Block Picture. . . . . . . . . . .. 185
6.4.1 Effects of Conjugation . . . . . . . . . . . . . . . . . .. 185
6.4.2 n* Bond-Bond Interactions . . . . . . . . . . . . . . .. 185
6.4.3 a* Bond-Bond Interactions. . . . . . . . . . . . . . .. 190
6.4.4 Aromatic Rings: Benzene and Related Molecules ... 199
6.4.5 Crystalline Solids . . . . . . . . . . . . . . . . . . . . .. 202
6.4.6 Effects of Core Hole Localization. . . . . . . . . . . .. 205
6.5 Assembly of Functional Groups to Macromolecules. . . . .. 207
7. Analysis of K-Shell Excitation Spectra by Curve Fitting . . . . . .. 211
7.1 The Need for a Quantitative Analysis . . . . . . . . . . . . .. 211
7.1.1 Curve Fitting of Original Spectra. . . . . . . . . . . .. 211
7.1.2 Curve Fitting of Difference Spectra. . . . . . . . . . .. 212
XIV Contents

7.2 Lineshapes of NEXAFS Resonances. . . . . . . . . . . . . .. 213

7.2.1 Gaussian, Lorentzian and Voigt Functions. . . . . .. 213
7.2.2 Asymmetric Gaussian and Lorentzian Lineshapes . .. 214
7.2.3 Giant Resonance Lineshape . . . . . . . . . . . . . . .. 219
7.2.4 Giant Resonance Versus Asymmetric Gaussian
Lineshapes . . . . . . . . . . . . . . . . . . . . . . . . . 221
7.3 Lineshapes of NEXAFS Steps. . . . . . . . . . . . . 222
7.3.1 Origin of Steps. . . . . . . . . . . . . . . . . . 222
7.3.2 Gaussian and Lorentzian Shaped Steps . . . 223
7.4 Examples of Steps. . . . . . . . . . . . . . . . . . . . 225
7.4.1 Continuum Steps for Free Molecules. . . . . . . . . . 225
7.4.2 Continuum Steps for Condensed Molecules,
Polymers, and Solids . . . . . . . . . . . . . . . . . . 228
7.4.3 Steps for Physisorbed and Chemisorbed Molecules 231
8. a* Resonance Position and Bond Length . . . . . . . . . . . . . . .. 239
8.1 Theoretical Predictions and the Search for a Correlation . .. 239
8.2 Predictions by Scattering Theory . . . . . . . . . . 242
8.3 Predictions by Molecular Orbital Theory . . . . . 245
8.4 Empirical Correlation for Simple Free Molecules 249
8.4.1 The Energy Reference Question. . . . . . . 250
8.4.2 Bonds Involving High-Z Atoms. . . . . . . . . . . . 252
8.5 Correlation for Large Molecules . . . . . . . . . . . . . . . .. 255
8.5.1 Chain-Like Hydrocarbons with Alternating Bonds .. 255
8.5.2 Non-aromatic Hydrocarbon Rings . . . . . . . . . . . 258
8.5.3 a-Conjugated and Aromatic Molecules . . . . . . 260
8.6 Extension to Condensed, Physisorbed,
and Chemisorbed Molecules. . . . . . . . . . . . . . . . . 264
8.6.1 Chemical Shifts and Resonance Positions. . . . . . .. 265
8.6.2 Weakly Adsorbed Molecules. . . . . . . . . . . . . . .. 267
8.6.3 Strongly Adsorbed Molecules Without Bonding Shifts 269
8.6.4 Strongly Adsorbed Molecules with Bonding Shifts. . 271
8.6.5 General Rules, Comments and the Use of Standards 272
9. The Angular Dependence of Resonance Intensities. . . . . . . . . . 276
9.1 Classification of Molecules. . . . . . . . . . . . . . . . . . 276
9.2 Resonance Intensities for Elliptically Polarized X-Rays . . .. 277
9.3 Angular Dependence of the Transition Matrix Elements . .. 279
9.4 Effect of Substrate Symmetry . . . . . . . . . . . . . . . . . .. 283
9.4.1 General Considerations. . . . . . . . . . . . . . 283
9.4.2 Twofold or Higher Substrate Symmetry. . . . . . . .. 283
9.4.3 Threefold or Higher Substrate Symmetry . . . . . . .. 284
9.5 Intensity Plots for n* and a* Vector Orbitals . . . . . . . . . 285
9.6 Intensity Plots for n* and a* Orbitals in a Plane ... . . .. 287
9.7 An Example: The n* Resonance Intensity in Graphite ... 288
9.8 Angular Dependence of Intensities in Difference Spectra . .. 290
 Contents XV

10. Selected Applications of NEXAFS. . . . . . . . . . . . . . . . . . .. 292

10.1 What Can We Hope to Learn? . . . . . . . . . . . . . . . . .. 292
10.2 CO on Pt(111) and the Effects of Na and H2 . . . . . . . . .. 295
10.2.1 CO/Pt(111) and CO/Na/Pt(111) . . . . . . . . . . .. 295
10.2.2 CO/Pt(l11) in the Presence of H2 Gas. . . . . . . .. 299
10.3 Molecular Oxygen on Pt(111) and Ag(110) . . . . . . . . . .. 301
10.3.1 Physisorbed Versus Chemisorbed 02 on Pt(l11) . .. 302
10.3.2 Chemisorbed 02 on Ag(llO) . . . . . . . . . . . . . .. 306
10.3.3 Hybridization and Bond Length. . . . . . . . . . . .. 307
10.4 The Bonding of Simple Hydrocarbons on Metals . . . . . .. 309
10.4.1 Bonding and Orientation of C 2 on Ag(110) . . . . .. 310
10.4.2 Di-sigma Bonded C 2H 4 on Pt(111). . . . . . . . . .. 315
10.5 The Bonding of Phenyl-Ring-Based Molecules
to Metal Surfaces . . . . . . . . . . . . . . . . . . . . . . . . .. 317
10.5.1 General Comments . . . . . . . . . . . . . . . . . . .. 317
10.5.2 Benzene........................... 319
10.5.3 Phenyl Thiolate and Phenoxide . . . . . . . . . . . .. 322
10.5.4 Pyridine........................... 325
10.5.5 Reaction Intermediates: Benzyne. . . . . . . . . . . .. 327
10.6 Thiophene on Pt (111) and Poly thiophene on Pt . . . . . . .. 329
10.7 Langmuir-Blodgett Chains on Si(111) . . . . . . . . . . . . .. 333
10.7.1 Experimental Results . . . . . . . . . . . . . . . . . .. 334
10.7.2 Chain Tilt, Intra-Chain Bonding,
and Origin of Resonances . . . . . . . . . . . . . . . . 337
10.7.3 Analysis of Difference Spectra . . . . . . . . . . . . .. 337
10.7.4 Curve Fits of Original Spectra. . . . . . . . . . . . .. 338
10.7.5 Structural Results . . . . . . . . . . . . . . . . . . . .. 340
11. A Look into the Future . . . . . . . .. . . . . . . . . . . . . . . . .. 342
11.1 Micro-NEXAFS.......................... 342
11.2 Liquid Surfaces. . . . . . . . . . . . . . . . . . . . . . . . . .. 343
11.3 Time-Resolved Studies. . . . . . . . . . . . . . . . . . . . . .. 344
11.4 Monosized Cluster Ions. . . . . . . . . . . . . . . . . . . . .. 345
11.5 Molecular Subgroups in Complex Environments . . . . . .. 347
Appendices. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
A. Derivation of the EXAFS Equation. . . . . . . . . . . . . . . . . . 349
B. Chemisorbed Molecules Studied by NEXAFS. . . . . . . . . . . . 359
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
Listing of Illustrated K-Shell Spectra . . . . . . . . . . . . . . . . . . . . . . 401
1. Introduction

In this first chapter we outline the reasons for writing a book about the near
edge X-ray absorption fine structure, or NEXAFS, technique, and explain why
the application of the technique to the study of molecules bonded to surfaces is
particularly important and interesting. A historical perspective of the develop-
ment of NEXAFS spectroscopy is also given.

1.1 Why Another Spectroscopy and Another Book?

Our century has been marked by the success of X-ray diffraction in revealing the
atomic structure of matter. Some of the most remarkable examples of this
success are the detailed structure determinations of complex macromolecules
that are the basis of life. The protein myoglobin, for example, which transports
oxygen in muscle, consists of a long twisted polypeptide chain in the form of a
so-called oc helix, as illustrated in Fig. 1.1. Especially remarkable is that the
landmark structure determinations shown in Fig. Ll and that of the well-known
molecule of heredity, deoxyribonucleic acid, or DNA, were accomplished in the
1950s [Ll]. At a time when the structures of macromolecules of such complexity
have been known for more than 30 years it would seem a trivial task to
determine the local geometry of a simple diatomic like O 2 bonded to the surface
of a material. Unfortunately and very surprisingly this is not the case. Surface
crystallography is still in a development stage and the answers to many
conceptually simple problems, such as the local structural geometry of a
chemisorbed molecule, still evade us. This is largely due to the fact that surface
science problems deal with a low abundance of species and in many cases a lack
of periodicity, which renders the tool of choice for bulk crystallography, X-ray
diffraction, of limited value. In fact, to date not a single structural determination
of a chemisorbed molecule has been performed using this technique.
In general, only a handful of structural determinations of molecules on
surfaces have been carried out, mostly by means of low energy electron diffrac-
tion (LEED) [1.2]. This is a striking deficit in light of the importance of the
problem. After all, water and our atmosphere consist of molecules and therefore
molecule-surface interactions are ever-present phenomena in our world, in fact,
they are the origin of life. For example, the bonding of O 2 to the heme group
(Fig. Ll) in myoglobin and hemoglobin is the basis of oxygen transport in
 N
Helical thread Backbone of N, Entire helix High resolution model
with a-carbon a-C and carbonyl
atoms C atoms :-
go
3Q.
c:
~
o·
:>

oM ~ N

Heme group

sA

Fig. 1.1. Microscopic structure of Ct: helix, an important structural motif in many proteins, and of the
protein myoglobin, taken from the textbook by Stryer [1.1]. The tightly coiled Ct: helix was proposed
by Pauling and Corey in 1951 as one possible conformation of polypeptide chains. It underlies the
structures of the oxygen carriers myoglobin and hemoglobin whose structures were solved by
Kendrewand Perutz, respectively, in the late I 950s. On the right is shown a high resolution model of
myoglobin which contains the oxygen-binding heme group. The O 2 molecules are bound in a bent,
end-on orientation to the iron atom in the center of the heme group shown at the bottom right
 1.1 Why Another Spectroscopy and Another Book? 3

muscle and blood [Ll]. The interactions of molecules with surfaces also play
key roles in modern technology. They underlie the multibillion dollar petroleum
industry serving the world's needs in gasoline and energy production. Here the
interaction of oil, which can be envisioned as large molecules consisting of
carbon and hydrogen atoms, with the surface of metal particles, so-called
catalysts, is used to process oil into high octane gasoline [1.3, 4]. Another
example is the important Haber-Bosch process, where hydrogen from water and
nitrogen from the atmosphere are converted into ammonia by an iron-based
catalyst [1.5]. Ammonia and its derivatives are widely used as fertilizers and for
the production of explosives, plastics, vitamins, and drugs. In high technology
areas, molecule-surface interactions are important in the preparation of semi-
conductor materials by reactive etching processes and they determine the
adhesion of thin polymer coatings used as insulators in the packaging process of
electronic devices [1.6] and as protective and lubricating overcoats on magnetic
recording media. In a more general and basic sense, the interaction of molecules
with surfaces creates fascinating molecular transformations and reactions whose
understanding is the essence of chemistry.
This book describes a new surface science technique which appears capable
of solving some of the problems in surface chemistry mentioned above. The near
edge X-ray absorption fine structure or, for short, NEXAFS technique was
developed in the 1980s with the goal of elucidating the structure of molecules
bonded to surfaces, in particular low-Z molecules. The term "low-Z molecules"
refers to mostly organic molecules containing important atomic building blocks
such as hydrogen, carbon, nitrogen, oxygen and fluorine. It is these molecules
that, for the technological reasons mentioned above, are of special interest in
surface science. NEXAFS is no panacea for all structural problems concerning
molecules bonded to surfaces but, as most techniques, has specific strengths and
weaknesses.
NEXAFS selects a specific atomic species through its K-edge and probes its
bonds to intra-molecular and, to a lesser degree, extra-molecular (i.e., surface
atoms) neighbors. Among the capabilities are: the ability to detect the presence
of specific bonds in molecules (e.g., C-C, C=C, C=C, and C-H bonds in
hydrocarbons), the determination of the lengths of these intra-molecular bonds
and the derivation of the precise orientation of molecules and functional groups
on surfaces or in solids. By comparison of spectra for free and chemisorbed
molecules NEXAFS can also reveal which orbitals are involved in the chemi-
sorption bond. To first order it gives no information on the detailed atomic
adsorbate-substrate registry. This part of the problem can, however, be solved
with the related and complementary surface extended X-ray absorption fine
structure (SEXAFS) technique [1.7, 8]. Nevertheless, NEXAFS by itself is a new
powerful surface structural tool which not only provides important information
but does so with conceptual and experimental ease.
The purpose of this book is to give a thorough and comprehensive review of
the principles, experimental techniques, and analysis methods of NEXAFS.
Such a review appears timely because the major development phase ofNEXAFS
4 1. Introduction

lies behind us and the commissioning and construction of new synchrotron

radiation facilities around the world will enable an increasing number of
scientists to use the technique. Besides discussing the NEXAFS technique itself,
this volume also presents several applications of NEXAFS for the study of
molecules bonded to surfaces (Chap. 10). Emphasis is given to the character-
ization of the behavior of different classes of molecules upon chemisorption. The
book would not be complete without a look at the prospects of novel scientific
applications of the technique, which is provided in the last chapter. The various
molecular chemisorption systems studied by NEXAFS are tabulated in
Appendix B.

1.2 Development of the NEXAFS Technique

After revealing the shell structure of atoms at the beginning of this century,
X-ray absorption spectroscopy was first used in the 1920s for structural invest-
igations of matter. The observed fine structure near the absorption edges was
first explained in general terms by a theory of Kossel [1.9] and for many years
was referred to as "Kossel structure". In contrast, the structure extending for
hundreds of electron volts past the edge was called "Kronig structure" after the
scientist [1.10] who germinated its theoretical explanation. The latter is, of
course, what is now called extended X-ray absorption fine structure (EXAFS)
[1.11].
During the 1970s, when EXAFS was developed into a powerful structural
tool, the near edge structure which was automatically recorded with every
EXAFS spectrum was largely discarded as too complicated. One exception was
the near edge structure oflow-Z molecules whose K-shells with binding energies
in the 250-750 eV range (carbon: 285 eV, nitrogen: 400 eV, oxygen: 535 eV, and
fluorine: 685 eV) could be conveniently excited by electron energy loss spectro-
scopy [1.12, 13], as discussed in detail in Chap. 4. The high quality K-shell
excitation spectrum ofN2 recorded with inner shell electron energy loss spectro-
scopy (ISEELS) [1.14] served as the input for the first quantitative calculation of
the near edge structure of a molecule, performed by Dehmer and Dill in 1975
[1.15]. Since then significant progress in the understanding of the near edge
structure in molecules, inorganic complexes, biological systems, crystalline and
disordered solids, and chemisorbed atoms and molecules has been made
[1.16-18], and we are now in a position to use it as a structural tool.
In recent years the Kronig near edge structure has been mostly referred to as
the X-ray absorption near edge structure, XANES, [1.19] or the near edge X-ray
absorption fine structure, NEXAFS [1.20]. The term XANES is more com-
monly used for solids and inorganic complexes while NEXAFS is used more in
conjunction with surfaces. In fact, the name NEXAFS was created in part
because it rhymes with SEXAFS, the surface version of EXAFS [1.7, 8], and it
constitutes the first part of a SEXAFS spectrum. Alternatively, one can think of
 1.2 Development of the NEXAFS Technique 5

"N" EXAFS as "Not" EXAFS. In the following we shall use the term NEXAFS
specifically for K -shell excitation spectra of low-Z molecules adsorbed on
surfaces.
The general importance oflow-Z molecules is a consequence of their natural
abundance and their unique chemical bonding properties leading to myriads of
different molecules and organic compounds. The nature of the intramolecular
bonds also puts the low-Z molecules into a class of their own with respect to
their near edge structure. First, the strong directionality of the covalent bonds
between low-Z atoms coupled with the polarized nature of synchrotron radi-
ation leads to strongly polarization-dependent K-shell spectra for oriented
molecules. Secondly, the characteristically short bond lengths (1.1-1.5 A), the
strong dependence of the bond length on the hybridization of the bond, and the
large backscattering amplitude of low energy electrons from low-Z atoms
combine to create K-shell spectra with prominent, structure-sensitive reson-
ances in the first 30 eV above the edge.
This important fact is demonstrated in Fig. 1.2 for the C K-edge. The
molecules benzene (C6H6) and cyclohexane (C 6H 12 ) as well as the correspond-
ing bulk compounds graphite and diamond all exhibit large resonance-like
structures in the first 30 eV above the K-shell threshold (~285 eV) which are
significantly larger than the higher energy EXAFS oscillations. These reson-
ance-like structures are the topic of this book. As we shall see, near edge
structures are very sensitive to the intramolecular and chemisorptive bonding
and, most importantly, follow simple rules. These semiempirical rules, which
were aided or retroactively confirmed by theory, allow a theory-independent

Cyclohexane
Cs H12

Fig. 1.2. Carbon K-shell X-ray absorption

Diamond
spectra of solid benzene and cydohexane, con-
densed onto a substrate at 80 K, and of single
crystal diamond and highly oriented pyrolytic
graphite. All spectra were recorded in geo-
metries which eliminate polarization depend-
ent effects [1.21-23]. Note pronounced NEX-
AFS structure compared to the weaker EX-
Photon Energy (eV) AFS structure at higher energies
6 1. Introduction

interpretation of the observed near edge structures or resonances in most cases.

This makes the study oflow-Z molecules adsorbed on surfaces possibly the most
important application of near edge X-ray absorption spectroscopy.
The first NEXAFS spectrum of a chemisorbed molecule [CO on Ni(l00)]
was recorded in 1980 at the Stanford Synchrotron Radiation Laboratory and
published in conjunction with data for NO on Ni(l00) in 1981 [1.24]. The
motivation behind the first study was a comparison of the K-shell near edge
structures of chemisorbed CO and NO recorded by electron versus ion yield
detection [1.25]. Important prerequisites for the first NEXAFS measurements
were the availability of high-intensity monochromatic soft X-ray (250-1000 eV)
synchrotron radiation [1.26, 27] and the previous development of electron yield
detection techniques for SEXAFS measurements [1.26, 28-31]. The 1981 publi-
cation focused on the polarization dependence of the near edge resonances,
which was used to determine the molecular orientation on the surface. A more
detailed study of the spectra of CO, NO, and N2 on Ni(l00) published in 1982
[1.20] derived the equations for the angular dependence of the resonances
following the theory of Davenport [1.32] and Wallace and Dill [1.33] and
discussed the energetics of the observed NEXAFS resonances in terms of those
of the free molecules recorded earlier with ISEELS [1.12, 13].
In 1983 it was realized through the study of CO, formic acid (HCOOH), and
methanol (CH 3 0H) on Cu(l00) [1.34] that the position of the so-called "u shape
resonance" was a sensitive measure of the intramolecular bond length and in
conjunction with the existence and intensity of the lower energy "n resonance"
revealed the bond hybridization. With this study the sensitivity of NEXAFS to
the intramolecular structure and bonding was established. In the same year
NEXAFS was applied for the first time to the study of aromatic rings such as
benzene (C 6 H 6 ) and pyridine (CsHsN) chemisorbed on Pt(111) [1.35] and it
was demonstrated that the orientation of such molecules can be readily
determined.
The close correspondence between the spectra for gas and chemisorbed
molecules led to a closer inspection of the correlation between u resonance
position and bond length in 1984. Using the large data base available for the K-
shell ISEELS spectra of low-Z molecules [1.13] a simple empirical correlation
was established [1.36, 37] and extended to chemisorbed hydrocarbons by Stohr
et al. [1.38]. In particular, these authors pointed out that, because of the linear
nature of the correlation, bond lengths could be simply obtained from the
spectra by measuring with a ruler the separation of the u resonance position
from the onset of absorption.
The years 1984-1986 saw the use of NEXAFS to solve several important
surface science problems, like the desulfurization process of thiophene on
Pt(lll) [1.39], the structural transformation of ethylene to ethylidine on Pt(lll)
[1.40,41], the Na-induced bonding and bond length changes of CO on Pt(111)
[1.42], the observation of novel intermediates from methanethiol (CH 3 SH)
decomposition on Pt(111) [1.43], and the coverage dependent phase transition
of pyridine on Ag(lll) [1.44]. The latter study is especially noteworthy in that it
 1.2 Development of the NEXAFS Technique 7

was carried out in real time during continuous molecular adsorption on the
surface and therefore sets the stage for kinetic studies by means of NEXAFS.
An important development in NEXAFS instrumentation occurred during
1985-1986 with the first demonstration of fluorescence detection, first at the
sulfur K-edge (2470eV) [1.45, 46] and then at the carbon K-edge (285eV) [1.47,
48]. This enabled NEXAFS studies at ambient pressure under reaction condi-
tions [1.49].
One major development since 1986 lies in the application of NEXAFS and
also ISEELS [1.50-58] to increasingly more complex molecules, including thin
polymer films on surfaces [1.59-69] and the understanding of such spectra
through detailed calculations [1.70, 71]. The message emerging from these
studies is that the spectra of complex molecules can often be explained in a
simple building block picture by the superposition of the spectra of diatomic or
larger functional subgroups [1.71-73].
Another significant advance, made possible by the development of novel soft
X-ray monochromators [1.74, 75], is the study of condensed, physisorbed, and
chemisorbed molecules with high ( ~ 50 me V) energy resolution revealing vibra-
tional fine structure [1.76, 77]. Such studies also aided the identification of
magnetic effects in K -shell spectra, e.g., of the large exchange splitting of the (1 *
resonance in the O 2 molecule [1.78].
From all these studies it has become clear that NEXAFS is applicable to the
study of a large range of molecular systems, and in the following chapters the
principles, techniques, and applications of NEXAFS spectroscopy will be
presented.
2. Theory of Inner Shell Excitation Spectra

Below we review the fundamental aspects underlying the calculation of X-ray

absorption spectra. We emphasize approximations commonly made for the
calculation of transition energies and transition intensities and, in particular,
discuss two theoretical techniques which have been successfully applied for the
calculation of molecular X-ray absorption spectra.

2.1 Description of the X-Ray Absorption Process

2.1.1 The X-Ray Absorption Cross Section

The X-ray absorption cross section (Ix of an atom or molecule is defined as the
number of electrons excited per unit time divided by the number of incident
photons per unit time per unit area [2.1]. It therefore has the dimension
(length)2 and is usually given in units of cm 2 or barn (1 cm 2 = 1024 barn). The
cross section can be calculated from Fermi's "Golden Rule" for the transition
probability per unit time Pif from a state Ii) to a state If) driven by a harmonic
time-dependent perturbation V(t) = Ve- icot

(2.1)

where (!f(E) is the energy density of final states. In the case of a K-shell
excitation Pif is the number of electrons excited per unit time from the 1s shell
to a final state If) which, in principle, can be a bound or continuum state. Since
the term "cross section" usually refers to photoionization let us at this point
assume that If) describes a continuum state corresponding to a free electron in
the potential of an ion. The connection to bound final states, corresponding to
an excited electron trapped in the potential of an overall neutral atom or
molecule, will be made later.
In order to obtain the total X-ray absorption cross section at a given photon
energy we have to sum over all shells with binding energies less than hw.
However, since we are mainly interested in the partial absorption cross section
of inner shells and since all electrons in the outer shells have a smooth cross
section at inner-shell excitation energies, we shall for simplicity ignore the
underlying cross section contribution from the outer shells. The inner shell
 2.1 Description of the X-Ray Absorption Process 9

excitation is produced by an electromagnetic wave with electric field vector E

and vector potential A. It is common to work in the Coulomb gauge [2.2],
where the two quantities are related according to

E= _~ aA . (2.2)
e at
We can write the vector potential in the form of a plane electromagnetic
wave of wave vector k, frequency w, and unit vector e,

A = eAo cos(k. x - wt) = e ~o (ei(k'x - wt) +e- i(k·x - wt)) • (2.3)

The wave vector magnitude is related to the photon energy hw and the X-ray
wavelength A according to Ikl = hw/he = 2n/A. Equations (2.2) and (2.3) show
that A and E are collinear in space and their magnitudes are related by
Eo = Aow/e. The photon flux Fph associated with this plane wave, i.e., the
number of photons per unit time per unit area, is given by the energy flux of the
electromagnetic field [2.2] divided by the photon energy

A~w E~e
F h =--=--· (2.4)
p 8nhe 8nhw

In accordance with our earlier definition the X-ray absorption cross section is
then obtained as

(2.5)

Let us now evaluate Pif. The dominant perturbative term describing the
interaction of spinless particles of charge - e and mass m with an electromag-
netic field is given by [2.3 - 5]

e
V(t)=-A'p, (2.6)
me
where P = L,Pi is the sum of the linear momentum operators of the electrons.
Substituting (2.6) and (2.3) into (2.1), and realizing that only the time dependent
term e- irot in (2.3) causes transitions that absorb energy (the other term would
induce emissions ifthe atom had an inner shell hole), we obtain for the transition
probability per unit time

(2.7)

We can simplify (2.7) by retaining only the first term in the expansion of the
exponential, the dipole approximation. This important approximation assumes
k' x ~ 1 or Ixl ~ A/2n, where A is the X-ray wavelength. For excitation of the
10 2. Theory of Inner Shell Excitation Spectra

oxygen K -shell at hw = 550 eV the wavelength is A./2n = 3.6 A and Ix I, charac-

terizing the K-shell diameter, can be estimated from the Bohr radius ao = 0.53 A
and the atomic number Z as Ixl ~ 2ao/Z = 0.13 A, so that the dipole approx-
imation is well satisfied. We then obtain the final result for the X-ray absorption
cross section [2.1, 5J,
4n 2 h 2 e2 1
Ux "";-2--h -h
mew
l<fl e ·pli)1 2 (>,(E). (2.8)

The expression for the energy density of final states, (>,(E), depends on the
normalization of the wavefunctions. Bound states have unit normalization while
continuum states are normalized to a Dirac delta function in the kinetic energy
E of the photoelectron [2.6]. Although it is known that the plane wave
description of the photoelectron is oversimplified and does not give accurate
cross sections, especially near threshold [2.7J, let us use it, nevertheless, to
illustrate the normalization of continuum states and the dimension of UX' For
simplicity we evaluate (2.8) in a one-electron model (Sect. 2.5.3). We write the
photoelectron wavefunction as

If> = L!/2 exp(iq'r), (2.9)

where q is the wavevector of the photoemitted electron and the function is

volume-normalized in a large cubic box of length L. This volume normalization
of the free electron wavefunction is similar to that ofthe initial core state Ii> such
that the dipole matrix element in (2.8) simply has the dimension of p2. For the
plane wave given by (2.9) the expression for the density of final states per unit
energy is given by the familiar expression [2.8J
L3 mq
(>f(E) = (2n)3 h2 . (2.10)

A quick check of the dimension of U x according to (2.8) verifies that the cross
section is indeed given in units of an area. The first term 4n 2 h 2 /m 2 has the
dimension (energy x length 2 /mass), the second e2 /hc = 1/137.04 is the dimen-
sionless fine structure constant, the third l/hw and the last (>,(E) have the
dimension (l/energy), and the matrix element has the dimension of p2, or
(energy x mass).
Other forms of the dipole matrix element in (2.8) can be obtained by use of
operator equivalents for the total linear momentum operator [2.9J
'h im(E f - Ea ih 17V (2.11)
P = mv = -1 J7 = r = ",
h Ef - E;
where v and r are the sum of electron velocities and positions, J7 is the sum
of the gradient operators and V is the potential energy represented by the
electron-nuclear attraction and electron--electron repulsion terms in the Hamil-
tonian of the atom or molecule. Sometimes the matrix element is written using
 2.1 Description of the X-Ray Absorption Process 11

the "dipole operator" p. = er. The dipole matrix element with one of the first
three operators is usually referred to as the "velocity" form, the matrix element
with the position operator is termed the "length" form and the last expression is
called the "acceleration" form. In principle, hw = E f - E;, but it should be
remembered that hw is an experimental quantity, while E f and E; are, in
principle, eigenvalues of an approximate Hamiltonian. Similarly, the matrix
elements for different operators are only identical if the wavefunctions are exact
eigenstates of the total electronic Hamiltonian. For approximate eigenfunctions
the matrix elements differ according to the quality of the wavefunctions in
different regions of space [2.9].

2.1.2 Optical Oscillator Strength and Sum Rules

For discussion of transitions to bound states and intensities of resonances it is
convenient to define a dimensionless quantity, the optical oscillator strength f
which is related to the X-ray absorption cross section according to [2.10]

df
(1'.(E) = c dE' (2.12)

where C = 2n 2 e 2 h/mc = 1.1 x 10 2 MbeV. Since fis the energy integral of the
cross section, the oscillator strength is a measure of the intensity of a resonance
and the intensities of bound state transitions are typically quoted as an
"f number",
2
f I<fle·pli)1 2
= -h-
mw
• (2.13)

In comparing calculated bound and continuum intensities and in their

comparison to measured spectra, care has to be taken in properly normalizing
them to each other. Since continuum structures are typically broader than
the instrumental resolution the calculated continuum cross sections can be
directly compared to experiment. The calculated oscillator strengths for bound
state transitions can be converted to cross sections by use of (2.12) and
introduction of an energy density [2.1, 10, 11]

2n 2 e 2 h
(1'x(E) = f (1b(E) , (2.14)
mc

where (1b(E) is the bound state energy density of final states. As the excitation
energy approaches the ionization potential (IP) the bound state cross section
merges into the continuum cross section through ever closer-spaced Rydberg
states as illustrated in Fig. 2.1a for K-shell excitation in helium gas [2.12]. At the
IP, (2.14) is formally identical to the continuum cross section given by (2.8) if we
set l?b(E) = (1f(E). In a cross section versus energy plot the height of a bound
state resonance is given by (1'. and the width by 1/l?b such that the intensity or
12 2. Theory of Inner Shell Excitation Spectra

Fig. 2.1a, b. Illustration of the Is -+ np Rydberg ser-

104 (a) 1s-np IP ies in helium and argon gas, merging into the ioniza-
tion continuum at the Is ionization potential (IP). (a)
He 24.6eV High resolution (FWHM :::: 20meV) electron energy
.~
m
103
"0 c:
loss spectrum of 25keV electrons, recorded in the
0>2
~ c: dipole excitation limit of small momentum transfer,
2- near the K-shell excitation threshold (IP = 24.6eV)
co g 10 2 in He gas [2.12]. (b) X-ray absorption spectrum of
~!:
u
0>
Ar gas near the K-shell threshold (IP = [Link])
W 10 [2.13, 14]. Also shown as dashed curves is a fit using
Lorentzians to describe the Rydberg resonances
at the IP. In both spectra the widths of the Ryd-
berg peaks originate mainly from the final state
I lifetime, the instrumental broadening being small.
(b) I
[Link] Note logarithmic intensity scale in (a) and linear scale
c: I
0 Ar in (b)
I
~c I
o~ ._
0>
I
m u
.n .- I
ct::::
0> 0.5
>-0
taO
a:I
x

0
-6 -4 -2 0 2
Excitation Energy - IP (eV)

area of the peak is equal to the oscillator strength. Discrete transitions are often
very narrow and the measured peak height depends on the lineshape and width
of the peak. This is clearly revealed by a comparison of Rydberg transitions in
the helium and argon [2.13] K -shell spectra shown in Fig. 2.1. In both spectra
the width of the discrete resonances is mostly determined by the Lorentzian
lifetime width ofthe electronic final state, the Gaussian instrumental broadening
being small. The larger lifetime width for argon [2.15,16] thus leads to a reduced
Rydberg peak height relative to the continuum step at the IP. Comparison of
experiment with theory therefore necessitates conversion of the calculated
oscillator strength into an appropriately shaped peak keeping the area of the
peak, i.e., the oscillator strength, constant.
The discrete and continuum oscillator strengths satisfy some important sum
rules [2.10, 17, 18], the best known of which is the Thomas-Reiche-Kuhn sum
rule. It states that for a given electron in an atom or molecule the sum of the
oscillator strengths of all transitions to all other states, discrete and continuous,
occupied and unoccupied, is unity. It then follows that the total oscillator
strength for the electronic excitation of an atom or molecule is equal to the
number of electrons N in the atom or molecule, i.e.,

(2.15)
 2.2 Time Scales in Inner-Shell Excitations 13

The first term in (2.15) represents the intensities of the discrete resonances below
the IP, i.e., absorption edge, arising from the various electronic shells of the
atom or molecule while the second term is the intensity above the IP. Hence if
one plots df(E)/dE as a function of energy E, including the discrete part of the
spectrum, the area under the curve is proportional to the number of electrons in
the atomic or molecular system. Equation (2.15) is also approximately valid for a
given subshell of an atom, e.g., the K-shell. In this case the integration in (2.15)
extends over energies above the respective IP of the subshell, after subtraction of
the background from lower binding energy shells, and N is the number of
electrons in the subshell. Wheeler and Bearden [2.17] have considered the K-
shell oscillator strengths of low-Z atoms and pointed out that, in practice, N is
less than the expected value of 2 because excitations to occupied valence orbitals
are excluded by the Pauli principle. Deviations from the values expected from
the sum rule have also been noted by other authors [2.19, 20].

2.2 Time Scales in Inner-Shell Excitations

The theoretical description of the X-ray absorption process in atoms and

molecules requires knowledge of electronic energies and wavefunctions. For an
explanation of the most detailed features nuclear vibrations must also be
considered. Before entering into a mathematical treatment let us first consider
the time scales involved in electronic excitations and nuclear motions. Sudden
vertical electronic excitation caused by the electric field of a photon occurs in the
time that it takes the photon to travel the diameter d of the inner shell. With
c = 3 X 10 18 A/s and d ~ 0.1 A for the K-shell of oxygen we can estimate that the
excitation takes place in about 10 - 17 to 10- 18 s.

2.2.1 Electron and Hole Lifetimes

The excitation leads to a molecule in a nonequilibrium state subject to electronic
rearrangements and nuclear motions. Resonances in inner shell excitation
spectra correspond to an excitation from an initial to a resonant final state. The
full width of the resonance r is determined by the lifetime of the final state 't
according to the Heisenberg uncertainty principle r ~ h/'t. In discussing X-ray
absorption spectra it is convenient to separate 't into two contributions, the
resonance "lifetime" of the excited electron within the molecular potential 't e and
the lifetime of the inner-shell hole state 'th, according to

1 1 1
-=-+-. (2.16)
't 't e 'th

Note that the separation of the core hole and electron lifetimes used in (2.16)
relies on a somewhat simplified model. For example, there is evidence that the
14 2. Theory of Inner Shell Excitation Spectra

core hole lifetime in a given molecule depends on the excitation energy

[2.21, 22].
The inner-shell hole lifetime can be estimated in two ways. Using high
resolution X-ray absorption spectra, we can estimate 'h from the measured
lifetime width r of a bound state resonance since such a transition is character-
ized by 'e = 00. The measured width r is related to the hole lifetime by the
uncertainty relation 'hr ~ h = 6.6 x 1O- 16 eVs. Alternatively, we can use
photoemission spectroscopy [2.23]. In the limit of negligible instrumental
broadening the width of the inner-shell photoemission peak, i.e., the measured
kinetic energy distribution of the inner-shell photoelectron, is also determined
'h
by according to the above uncertainty relation.
Hole lifetime widths of low-Z atoms for the K and L3 shells have been
estimated by Parratt and Brown [2.14,24] and Krause and Oliver [2.15,16] and
are shown in Fig. 2.2. Note that the bound state lifetime widths correspond to
the total hole lifetime according to l/'h = l/'a + 1/,J where for low-Z atoms the
Auger lifetime 'a is much shorter than the fluorescence lifetime, J [2.15]. If we
use a hole lifetime width of r ~ 0.1 eV for the K-shell of a nitrogen atom
we obtain a characteristic lifetime in the 1O- 15 _1O- 14 s range. In contrast
to bound state resonances, the width of continuum resonances is determined by
'e' the lifetime of the resonantly trapped electron. Using a value of 10eV for
a characteristic continuum resonance width we obtain a lifetime in the
10- 17_10- 16 s range. Hence the longer lived core hole will influence the trapped
photoelectron.

Natural Width 01 Core Levels

Mo

:> 1.0
~
.c
'0
3
-.; Fig. 2.2. Full width at half maximum
>
for the K and L3 levels of the lighter
'"
..J
elements as a function of photon en-
I
I
ergy as estimated by Parratt [2.14]
I
I
I
and plotted by Brown [2.24]. The
I
dashed lines are semiempirical values
0.01 ~"""--'---'--J._"--..l...--'---'----'_'--"""--'----'
o 400 800 1200 1600 2000 2400 taken from the tables of Krause and
Photon Energy (eV) Oliver [2.15, 16]

2.2.2 Separation of Electronic and Nuclear Degrees of Freedom

Compared to the total lifetime of the electronic final state, the vibrational
motions of the nuclei are slow because of their large mass (the ratio of proton
and electron masses is 1836) and typically occur in approximately 10- 13 s. This
 2.3 The Electronic Ground State 15

allows separation of the electronic and nuclear degrees of freedom, the

Born-Oppenheimer approximation [2.25], and solution of the Schrodinger equa-
tion for a fixed geometry (usually the ground-state equilibrium geometry) of the
molecule. Furthermore, the Franck-Condon principle [2.26] can be employed,
which states that the internuclear distance can be assumed to be constant during
the fast electronic excitation process.
We shall now consider electronic wavefunctions and energies needed to
calculate the X-ray absorption spectrum. They are, of course, obtained as
solutions of the Schrodinger equation for the molecular potential. Of particular
interest are resonances in the cross section near the K-shell excitation threshold.
Such resonances arise at certain transition energies which correspond to the
promotion of a Is core electron from the molecular ground state to a bound or
quasi-bound excited state. Calculation of these spectral resonance features
according to (2.8) requires the following: (1) the wavefunction of the molecule
in its ground state, (2) the wavefunctions of the bound and/or quasi-bound
(continuum) final states, and (3) the energy differences between the ground state
and the various resonant excited states. The wavefunctions determine the
transition intensities via the dipole matrix element while the energy differences
give the transition energies. Below we discuss how the necessary energies and
wavefunctions can be obtained. We shall start by discussing the electronic
ground state and then later deal with the more complex aspects of excited states.

2.3 The Electronic Ground State

2.3.1 The Hartree-Fock Method
According to the Born-Oppenheimer approximation, the total wavefunction for
a molecule consisting of N electrons and P nuclei can be separated into a
product of an electronic and a nuclear part,
(2.17)

and the Schrodinger equation for the electrons is

(2.18)

Here the Hamiltonian, in which we ignore relativistic and spin-orbit effects, is

written in an internal coordinate system such that the nuclear kinetic energy
term does not enter and is given by

+ L L zzlie
P P
I
2
(2.19}
1=111>1 Rill
16 2. Theory of Inner Shell Excitation Spectra

The different sums are the electron kinetic energy, the electron-nuclear attrac-
tion, the electron-electron repulsion, and the nuclear-nuclear repulsion terms,
and m is the electronic mass, e the electronic charge, and Z,e the charge ofthe lth
nucleus. The denominators rin = Iri - Rnl, rik = Iri - rkl, and R'n = IR, - Rnl
specify distances between electronic (rJ and/or nuclear (Ri) coordinates. The
solutions lJIe and Eo of(2.18) are parametric functions of the nuclear positions. If
the Schrodinger equation is solved as a function of the internuclear separations,
Eo = Eo(R'n) can provide the potential in which the nuclei move. The solution
to a second Schrodinger equation for the nuclear motion then yields vibrational
energies EVib and wavefunctions ifJvib(R) for the molecule as shown in Fig. 2.3.
For example, for a diatomic molecule the total energy as a function of inter-
nuclear distance, Eo(R), often approximates the form for a harmonic oscillator.
Then

(2.20)
where Wvib is the classical vibration frequency and v = 0, 1, 2, ... is the vibra-
tional quantum number. Rotational splittings are typically too small to be
resolvable in K-shell spectra. For excitations of core electrons the equilibrium
internuclear distance in the electronic ground and excited states may be slightly
different as shown in Fig. 2.3. According to the Franck-Condon principle, in a
vertical transition only those vibrational levels vf of the excited electronic state
can be reached whose eigenfunctions have nonvanishing overlap with the
wavefunction of the lowest vibrational state of the electronic ground state Vi = O.
A common starting point for obtaining reasonably accurate wavefunctions
for electrons in ground states of atoms and molecules is the Hartree-Fock (HF)
self-consistent-field (SCF) method [2.27]. The HF equations are derived from the
quantum mechanical variation principle. lJIe is approximated by a single Slater
determinant IJI of N orthonormal one-electron spin-orbitals <Pi [2.28],

(2.21)

If the expectation value of the total energy,

(2.22)

is calculated from an approximate solution IJI of the SchrOdinger equation then

Eo is always greater than the exact ground state energy Eo for the Hamiltonian.
The difference

(2.23)

is called the correlation energy and reflects the fact that correlation, i.e., the
dependence of the motion of one electron on the position of a second electron,
cannot be represented by a simple product of functions of individual electron
 2.3 The Electronic Ground State 17

a::
a
w
>-
Ol
Q;
c:
w
iii
~
o
Q)

Cl.

Internuclear Distance R

Fig. 2.3. Illustration of the Franck-Condon principle. Through X-ray absorption a molecule X Y
undergoes an electronic transition from an initial state (the K-shell) to a bound final state (a Rydberg
or unfilled valence orbital). For the initial and final electronic states the potential in which the nuclei
move is given by the energies Eo( R) obtained from the Schrodinger equation (2.18) for the molecular
ground (XY) and the core excited (XY*) states, respectively, as a function of the internuclear
separation R. In case A the potential for the ground and excited states have a minimum at the same
internuclear distance R, while for the excited state in case B the minimum falls at a larger R value.
The Franck-Condon principle states that during an electronic transition the internuclear distance
can be assumed to be constant. Therefore only those vibrational states Evib ( vf) of the excited
electronic state can be reached in a "vertical" electronic transition from the vibrational ground state
Evib ( Vi = 0) whose wavefunctions I/Ivib( vf, R) have a finite overlap with those of the electronic
ground state I/Ivib(V i = 0, R). The overlap integral is the Franck-Condon factor given by (2.49). The
range of internuclear distances spanned by the ground state vibrational wavefunction is shown
shaded. For case A, maximum wavefunction overlap occurs for the vf = 0 excited state, while for the
higher vibrational states the overlap is nearly zero, owing to similar positive and negative
contributions. For case B, the overlap is largest for the first excited vibrational state vf = 1 with
finite, but smaller, contributions from vf = 0 and vf = 2. Note that vibrational splittings in X-ray
absorption are only observed iQ cases where the electronic lifetime r, given by (2.16), is sufficiently
long that the lifetime width is smaller than the separation between the vibrational levels of the
excited state

coordinates as given by (2.21) [2.29]. If by variation of the 4J/s the total energy
Eo is minimized we obtain N Hartree-Fock equations. The equation for the ith
electron at site x 1 with spin orbital 4Ji( x d is given by

(2.24)
18 2. Theory of Inner Shell Excitation Spectra

For a molecule consisting of P different nuclei, the Fock operator F is given by

[2.30]

(2.25)

where the Coulomb operator Jk , defined by the operation

(2.26)

gives the average repulsive Coulombic potential energy between all the electrons
in the system and the electron at position Xl' and the exchange operator, defined
as

(2.27)

takes account of the spin correlation according to the Pauli principle. This latter
term is a consequence of the tendency of electrons with like spins to avoid one
another, lowering, on the average, the Coulomb repulsion between them. The
wavefunctions depend on spin such that the terms in (2.27) vanish unless tPi and
tPk correspond to spins in the same direction.
For spectroscopists, it is a special form of the HF equations, namely the
diagonal or canonic form, which is offundamental importance. Fortunately it is
always possible to find a unitary transformation of the orbitals tPi under which
the Fock operator, the total wavefunction P, and the total energy Eo are
invariant, such that the right-hand side of (2.24) is brought into diagonal form
[2.31]. This yields the canonical HF equations

(2.28)

The orbitals tPi are called canonical orbitals and they have an orbital energy Ei.
In practice, the HF equations are solved in the canonical form and for this
reason we shall use the term "molecular orbitals" or "MOs" in the sense of
canonical molecular orbitals. The significance of the canonical HF equations for
the interpretation of spectroscopic data will be discussed in more detail later.
Since Jk and Kk depend on all tPi'S, the integrodifferential equations (2.28)
have to be solved self-consistently. This involves the evaluation of matrix
elements of the Fock operator,

N
= Hii + L (J ik -
k=l
K ik ) , (2.29)
 2.3 The Electronic Ground State 19

where we have introduced the following integrals:

(2.30)

2
lik = JJ<p~(Xd<P:(X2) ~
r 12
<Pt(X 2)<Pi(x 1 )dx2dx 1 , (2.31)

and
2
Kik = JJ<p~(Xd<P:(X2) ~ <Pi(X 2)<Pk(xddx2dx 1 • (2.32)
r 12

lik is called the two-electron Coulomb integral and Kik the two-electron exchange
integral. The iteration process is terminated when the difference in total energy

(2.33)

between two consecutive iterations is less than some threshold value. Note that,
because of the factor 1/2 in front of the Coulomb and exchange integrals in
(2.33), Eo cannot be obtained from a sum over the canonical eigenvalues Ei given
by (2.29), i.e., from photoemission binding energies (see below).

2.3.2 Roothaan-Hall and Semiempirical Methods

The most time-consuming part of a HF-SCF calculation is the evaluation of the
two-electron Coulomb and exchange integrals defined above. It is apparent that
the practicality of the HF method depends on the complexity (e.g., the types of
mathematical functions) and number of the spin-orbitals <Pi' For all but the
smallest molecules the numerical integration of the Fock matrix elements, which
needs to be carried out at each cycle of the iterative procedure, becomes very
impractical. For this reason, a method due to Roothaan [2.32] and Hall [2.33] is
used. In the Roothaan-Hall HF method the molecular orbitals <p;'s are ex-
panded in a basis set of M atomic orbitals X, according to
M
<Pi = L ailX,'
1= 1
(2.34)

The atomic orbitals, themselves solutions of the HF equations for the

individual atoms, are regarded asfixed and the variation in the HF procedure is
performed on the expansion coefficients ail' Thus the set of integrodifferential
equations of the Hartree-Fock formalism is reduced to a set of linear equations.
The physical justification for the above linear combination of atomic orbitals or
LCAO method is two-fold. Firstly, in the limit that the molecule is pulled apart
the MOs must converge smoothly into the set of atomic orbitals of the atoms.
20 2. Theory of Inner Shell Excitation Spectra

Secondly, the functional form of the MOs near the nuclei must be similar to the
functional form of the atomic orbitals of the individual atoms. In the limit of a
complete basis set the molecular orbitals found by this method approach those
obtained by the rigorous HF method.
It is clear that an important part of the Roothaan-Hall HF method is the
selection of a finite basis set which is flexible enough to accurately describe all
possible molecular orbitals [2.34J. In practice, the following types of basis sets
are used. The simplest, the minimal basis set, consists of one type of basis
function for each type of atomic orbital that is occupied by electrons in the
ground state of the atoms. As basis functions Slater-type orbitals or Gaussian-
type orbitals are usually used [2.27, 35]. A minimal basis set typically yields only
a qualitative picture ofthe molecular properties. A better description is provided
by use of a double-zeta [2.36J or triple-zeta basis set which consists of two or
three variationally independent basis functions for each occupied atomic orbital,
i.e., two or three times as many functions as in the minimal basis. Sometimes a
different set of basis functions is used for the inner (core) and outer (valence)
orbitals or for occupied and virtual (empty) orbitals. In particular, for the
description of virtual orbitals polarization and diffuse functions may be added.
Polarization functions provide higher angular momenta than needed for the
ground state of the individual atoms, e.g., p functions for hydrogen or d
functions for the second row elements boron through fluorine, and diffuse
functions have small exponential coefficients and therefore a large spatial extent.
For large molecules and large basis sets even the Roothaan-Hall HF method
leads to very time consuming calculations because approximately n4 two-
electron integrals of the form
2
JJxi(xdx;(X2)~
r 12
x,(x 2)xk(x 1 )dx 2dx 1 , (2.35)

need to be calculated, where n is the number of terms in the basis. One approach
to overcome this problem is to use empirical data to obtain some ofthe integrals
and ignore most of the rest, as done in the semiempirical methods such as
MINDO, CNDO, etc. [2.37, 38]. However, the accuracy of such methods is
often questionable and for many cases no good empirical parameters are
available. For this reason we shall not discuss or use semiempirical calculations
here.

2.4 Transition Energies

In the previous section we discussed techniques for obtaining the electronic

ground state energy and the Is initial state wavefunction or orbital. We shall
now take the next step and consider the energetics of electronic excitations. At
 2.4 Transition Energies 21

this point we shall restrict ourselves to bound state transitions in which the atom
or molecule is not ionized. The case of ionization, i.e., transitions to continuum
states, is discussed later. Before we continue, another point needs to be made. In
the following we shall often use the terms "states" and "orbitals". In principle, a
"state" is an observable, while an "orbital" is a theoretical construction. We shall
use the terms in this sense, noting that in quantum mechanics orbital configura-
tions are a convenient way of describing electronic states.
An important quantity in the discussion of K -shell excitation spectra is the
Is ionization potential, defined as the minimum energy necessary to excite a Is
electron to the continuum of states above the vacuum level. The ionization
potential IP(i), or binding energy Eb(i), associated with a particular electron i in
an atom or a molecule is conveniently measured by photoelectron spectroscopy
(PES) [2.23] as the difference between the exciting photon energy lim and the
kinetic energy of the photoelectron E kin , i.e., the energy position of the peak in
the PES spectrum,

IP(i) = Eb(i) = lim - Ekin • (2.36)

In K-shell X-ray absorption, the Is IP is the threshold energy (usually

characterized by an absorption step) for transitions to continuum states. In
contrast to PES, which directly measures the "free" photoelectron at photon
energies larger than the IP, the lowest energy transitions observed in X-ray
absorption spectroscopy occur at photon energies less than the IP. These bound
state transitions involve final states below the vacuum level. Such states arise
naturally as solutions of the Schrodinger equation for atoms and molecules and
they correspond to the well-known Rydberg orbitals which give rise to the sharp
pre-edge peaks in Fig. 2.1. Similarly, in core excited molecules unfilled or empty
(virtual) molecular orbitals can have orbital energies below the vacuum level
and transitions to such orbitals also require excitation energies less than the Is
IP (see later).

2.4.1 Koopmans' Theorem

The question arises how one may calculate the IP or the transition energies
associated with bound state transitions. In principle, this is straightforward if we
ignore electron correlation. All we need to calculate is the difference in total
energy between the initial (ground) and final (excited) electronic states according
to (2.33). For a bound state transition to a Rydberg state, an electron is removed
from the Is shell and inserted in a Rydberg orbital in the final state calculation;
for the calculation of the IP the final state is assumed to be that of an ion with an
electron missing from the K-shell. This scheme, usually referred to as ASCF, is
cumbersome and, in practice, approximations are employed which yield suffi-
ciently accurate results in a single calculation. These are discussed below.
The most famous approximation, Koopmans' theorem, links the IPs or
binding energies measured for valence and core electrons by PES to the orbital
22 2. Theory of Inner Shell Excitation Spectra

energies Ei calculated by means of the HF equation (2.28) for specific atomic or

molecular orbitals. It states that the binding energy or IP of an electron i is equal
to the negative of its orbital energy, E i • Koopmans' theorem is derived by
considering the difference in total energy between the ionized species (E et ) with
an electron missing from orbital i and the neutral species (Eo), which by
definition is the ionization potential IP(i). In contrast to the rigorous L\SCF
approach, however, Koopmans' approximation assumes that upon excitation,
i.e., removal of an electron from some orbital fiJi' none of the other fiJkS change,
i.e., they remain frozen. Then by use of (2.29) and (2.33) the difference in total
energy, i.e., the ionization potential, can be shown to satisfy the relation

IP(i) = Eet - Eo = - Ei . (2.37)

This result also follows logically from the definition of Ei (2.25, 28) as the sum of
the kinetic energy, the potential energy in the nuclear field and the average
interaction energy with all other electrons. For bound states, Ei is negative such
that the IP and the binding energy are positive.
For K-shell excitations of the second row atoms the frozen-orbital assump-
tion made in the derivation of Koopmans' theorem is inadequate and the
predicted binding energies err by 10-20eV [2.39-41]. To account for this error
it is common to introduce a relaxation energy correction L\ER in the comparison
of Ei with experimental binding energies. Other shortcomings of this approach
are the neglect of relativistic effects, accounted for by a correction Er [2.42] and
of correlation effects, except those introduced by the Pauli exclusion principle
(2.27). The correlation energy correction L\Ecor accounts for the difference in
energy stabilization of the final and initial states through configuration inter-
action [2.29], which would require description ofthe states by a linear combina-
tion of Slater determinants. Finally, for open shell systems multiplet structure
cannot be ignored and it is accounted for by a term L\Em' which can be
calculated from tabulated Slater integrals [2.43]. We can then write the follow-
ing expression linking experimental binding energies and theoretical quantities:

(2.38)

For the K-shells of carbon, nitrogen and oxygen the various corrections
have been calculated and their approximate values are L\ER ~ 15eV [2.39-41],
L\Ecor ~ 1 eV [2.29, 41], and L\Er ~ O.2eV [2.42]. For the open shell molecules
NO and O 2 the multiplet splitting of the Is photoemission peak is 2L\Em ~ 1 eV
[2.44]. We see that the relaxation correction is especially large and must be
accounted for in the calculation of K -shell spectra.
One method for including relaxation uses the so-called equivalent cores
approximation [2.45]. Here, it is assumed that outer electrons are affected by
ionization of a core electron in essentially the same way as they would be if the
nuclear charge were increased by one unit, i.e., by the "equivalent core" of the
next element in the periodic table.
 2.4 Transition Energies 23

2.4.2 The Transition State Method

A particularly important approximation in conjunction with calculations of K-
shell spectra by means of the X a multiple scattering method [2.46-48], dis-
cussed below, is the transition state or transition operator method, introduced by
Slater [2.46, 49], in which relaxation effects are treated by second order
perturbation theory. The technique was later generalized by Goscinski et al.
[2.50] and used in conjunction with conventional Hartree-Fock calculations
and by Williams et al. [2.51] to include higher-order perturbation terms.
To illustrate how the transition state method works, let us define occupation
numbers {n i } = (nl' n2 , ••• ,nN) for the N spin-orbitals <Pi' Following (2.33), the
total energy can be written as a function of the occupation numbers,
_ N 1 N N
EO(nl' ... ,nN) = if:l
niH jj +"2 if:l kf:l nink(Jik - K ik )

p P ZZ 2
+
,=L n>'
L 'R'ne n (2.39)
1

Let us now consider ionization of an electron from orbital <p,. In the initial
ground state the occupation numbers are {nil = (nl = 1, ... n, = 1, ... nN = 1),
while the final excited state is characterized by {ni} = (nl = 1, ... n, =
0, ... nN = 1). If we assume that there is no relaxation, the binding energy Eb(l)
is given by Koopmans' value,

(2.40)

Since all passive electron orbitals remain frozen as n, is changed, it is apparent

that in this approximation Eo, from (2.39), is a linear function of n, and therefore
(2.40) is equivalent to

Eb(l) = -E, = _ oEo(n,) . (2.41)

on,
Now let us allow for relaxation such that the total energy is minimized for
any excited state, characterized by a change in the occupation n, of the "active"
orbital <p,. We shall not only allow the extreme cases n, = 0 and n, = 1 but also
fictitious states described by a fractional occupation number. In the conven-
tional ~SCF formulation the relaxed binding energy, which according to (2.38)
is given by Eb(l) = - E, - LJER , is obtained as

(2.42)

where we have explicitly indicated with a superscript that all total energies are
calculated by allowing relaxation of the passive electrons. It is clear that in this
case the total energy is no longer a linear function of n,. For example, the
Coulomb and exchange integrals in (2.39) will change as n, changes. Let us
assume, however, that the total energy can be expressed by inclusion of the next
24 2. Theory of Inner Shell Excitation Spectra

higher term as a second order polynomial in n,. If we plot E~ as a function of n,

we see from (2.42) that the relaxed binding energy Eb(l) is given by the difference
of the values of the curve at n, = 0 and n 1 = 1, or alternatively, by the slope of
the chord connecting these two points on the curve. But for a parabola the slope
of a straight line between two points on the curve is equal to the slope of the
curve itself at midpoint. Thus in our case we obtain the simple result,

oEo(n,) I (2.43)
on, nr = 1/2 '

which accounts for relaxation to second order. In fact, higher-order corrections

can also be accounted for by taking the derivative in (2.43) at a different n, value
[2.51]. In practice, the relaxed binding energies are not obtained from (2.43) but
directly from the Hartree-Fock equations written in the transition operator form
[2.50]
h2 Z e2
vi - L _"- + L
P N
FT = - -2 nk ( Jk - K k ), (2.44)
m 11=1 rill k=l

where {nd = (nl = 1, .. n, = 1/2, .. nN = 1). In this method, the relaxed IP or

binding energy of a specific orbital is thus obtained in a single calculation by
adjusting the conventional Fock operator (2.25) to involve a fractional occupa-
tion number of that orbital.
The above discussion of the transition state method specifically referred to
the calculation of IPs or binding energies. In X-ray absorption, however, the
excited electron may remain bound in a Rydberg or unfilled molecular orbital
and the question arises as to how one calculates transition energies for such
"two level" cases, consisting of a hole in the Is orbital and an electron in an
"outer" orbital. In analogy to the "one level" case, the transition operator in
(2.44) is used with half an electron removed from the lower and half an electron
added to the upper orbital [2.52]. The transition energies are then simply the
differences of the "orbital energies" of the two levels. This approach, however,
involves a new calculation for each "outer" orbital.
To avoid this complication and to allow both bound and continuum state
calculations to be performed with the same potential, calculations may be
performed ignoring the excited electron and modifying only the oc~upation of
the Is orbital by one half. The effect of this simplification is illustrated in Fig. 2.4
for the case of the C K-shell excitation in CO, using an Xa. multiple scattering
formalism (see below) [2.53]. Here we have plotted the "orbital energies"
obtained by solving the X a. HF equations in the transition state form (2.44),
using the occupation numbers indicated in the figure. In case A, we have
calculated the IP (295.2 eV) of the C Is or 2a orbital in CO by removing half an
electron from the 2a orbital. We have also indicated the "orbital energy"
obtained for the empty 2n * orbital (- 7.9 eV) in the figure. In a second
calculation, case B, we have carried out a "two level" transition state calculation
by removing half an electron from the 2a and adding half an electron to the
 2.4 Transition Energies 25

A B
Fig. 2.4. XCl multiple scattering transition state calcu-
Vacuum Level
lation for the 20" and 21t· "orbital energies" in carbon
monoxide [2.53]. In case A the occupation number of the
20" orbital, i.e., the carbon Is orbital, was reduced by half
t 2.." an electron in the Fock operator (2.44), relative to the
>
~ I
ground state, and the resulting 20" "orbital energy" repre-
I sents the relaxed binding energy or IP (295.2eV) of that
>-E' I orbital. The 20" -+ 21t· transition energy, E~ = 287.3eV
I
'"c:
w I calculated for this case is close to that, E. = 285.7eV,
I calculated in the proper "two level" transition state for-
~
:e ~
I malism, case B, where half an electron has been removed
p I from the 20" and half an electron added to the 21t· orbital.
3 IP
I
IE~ E.. This justifies that, in practice, calculations are usually
en performed without adjusting the occupation number of
.g -280 I
I the upper orbital
·in
c:
I
I
~ I
I ~(2a)1Y,
o(.)
I

~(2a)1Y,

empty 2n* orbital. This calculation thus yields the Is -+ 2n* transition energy
(285.7 eV) as the difference between the two "orbital energies", - 3.1 eV for the
2n* and - 288.8 eV for the 20" orbitals. Note that in this case only the difference
in "orbital energies", not the energies themselves, are meaningful.
Thus in an attempt to properly account for the IP and the 20" -+ 2n*
transition energy one would use the IP = 295.2eV calculated for case A and the
transition energy E" = 285.7 eV calculated for case B. Comparison with experi-
ment shows that the calculated IP is 1.0eV lower and the calculated transition
energy 1.6eV lower than the measured values [2.54]. The most important point
about Fig. 2.4, however, is that the calculation for case A predicts the 20" -+ 2n *
transition energy within 1.6eV of the value calculated for case B (the proper
method), and therefore it justifies the use of scheme A for the calculation of K-
shell excitation spectra. In fact, in our example, the E" value calculated for case
A, labeled E~ in the figure, is fortuitously predicted to be exactly the experi-
mental value of 287.3 eV.
A final word of caution concerns the position of the 2n * orbital below the
vacuum level in the final, core excited state. This cannot be directly obtained .
from either calculation A or B in Fig. 2.4 but can be derived indirectly as the
difference between the 20" IP calculated for case A (295.2eV) and the 20" -+ 2n*
transition energy (285.7eV) calculated for case B. The value of -9.5eV ob-
tained thus is in good accord with rigorous ASCF calculations [2.55, 56] and the
9.7 eV 2n* binding energy of the equivalent core molecule NO [2.57]. A direct
way of deriving this energy by a transition state calculation would be to remove
a full electron from the 20" orbital and to allow half an electron to occupy the 2n *
orbital. This yields a transition state 2n* "orbital energy" of - 9.2eV [2.53].
26 2. Theory of Inner Shell Excitation Spectra

2.4.3 Localized Versus Delocalized Core Hole

Another question which needs to be addressed concerns the localized nature of
the core hole, the concomitant reduction of the molecular symmetry, and the
effect on the transition energies. This has been extensively discussed in the
literature [2.58-62], especially for molecules with several equivalent cores, e.g.,
benzene [2.63]. As shown by Cederbaum and Domcke [2.60], in principle,
localized as well as delocalized core hole calculations may provide similar
answers for the energies of molecular states because the relaxation energy of a
localized core hole is equal to the sum of relaxation energy and the change of
correlation energy due to relaxation of a delocalized core hole. In addition,
wavefunctions within the framework of the nuclear symmetry can be construc-
ted using either MOs for delocalized core hole states or a linear combination of
MOs for localized hole states.
In practice, it is easier to carry out localized calculations since the inclusion
of correlation effects requires sophisticated configuration interaction calcu-
lations. The difference between complete localization and delocalization of the
core hole during excitation into the a* shape resonance has been discussed by
Dill et al. [2.64] for the N2 molecule. For the calculation of the a* shape
resonance the lifetime of the trapped electron is shorter than that of the core hole
and therefore the hole will live long enough to influence the resonant photo-
electron. It was found that the cross section is relatively insensitive to the
treatment of the hole. However, the photoelectron asymmetry parameter was
found to depend on the localized or delocalized nature of the hole.

2.5 Transition Intensities

Let us now consider the wavefunctions needed to calculate X-ray absorption

cross sections according to (2.8). For molecules, the wa vefunctions Ii) and If)
and the momentum operator p will be given in a coordinate system fixed along
certain symmetry axes of the molecule; the matrix element depends on the
orientation of the X-ray polarization direction e in the molecular coordinate
system. While the effect of X-ray polarization will be discussed in detail in
Chap. 9, let us here for simplicity assume that the X-rays are linearly polarized
and the molecules are randomly oriented with respect to the polarization
direction e. The X-ray absorption cross section is then obtained by an average
over all molecular directions, and from (2.8) we obtain

Ux = C (}~~) ~ {1<fIPxli)1 2 + l<flp li)1 2 + l<fIPzli)1 2 }

y

= C (}~~) ~ l<flpli)1 2 , (2.45)

where we have defined the constant C = 4n 2/ie 21m2 c. In the following we shall
 2.5 Transition Intensities 27

for simplicity discuss only the dipole matrix element,

Dif = </lpli> . (2.46)

2.5.1 One-Electron Versus Multi-Electron Transitions

We must know what wavefunctions to use in the evaluation of the matrix
element. Electronic excitations are, in general, a multi-electron process since they
affect the total electronic configuration of the atom or molecule, and re-
membering that P = LPk is the sum of the momentum operators of the indi-
vidual electrons, see (2.6), we find that the matrix element in its general form is
given by

I
Dif = ( 'l'f(N) kt/k l'l'i(N) ) , (2.47)

where 'l'i(N) and 'l'f(N) are the Slater determinants for the initial ground state
and final excited state of the N-electron system, respectively. In particular,
'l'f(N) is a Slater determinant where the spin-orbitallPk that has lost an electron
has been replaced by a new spin-orbital characterizing the excited electron or by
a continuum function, and the other spin-orbitals have been allowed to adjust to
that change. To account for correlation effects it is insufficient to use a single
Slater determinant. If we allow electrons to occupy "excited" or virtual orbitals,
an infinite number of determinants can be formed and a "better" wavefunction
can be obtained by expansion in a series of such Slater determinants. This model
is called configuration interaction (el), and although it has a small effect on
binding energies as revealed by the relatively small correlation correction AEcoro
it is of importance for the calculation of the intensities of satellite peaks [2.41],
also called "shake-up", "many-electron", or "correlation" peaks [2.65]. In the
following we shall assume for simplicity that a single Slater determinant can be
used for the general description of the initial and final electronic states.

2.5.2 Effects of Nuclear Vibrations

In the calculation of the transition matrix element we can include the effects of
nuclear vibrations through the wavefunctions t/I~ib and t/ltib of the vibrational
states associated with the initial and final electronic potential (Fig. 2.3). The
total initial and final state wavefunctions, including the effects of vibrations, can
be written as a product of the electronic and vibrational functions, and neglect-
ing the influence of the perturbing X-ray radiation on the internuclear distance
R we can write

D!:fb =( I
'l'f(N)t/ltib(R) ktl Pkl t/I~ib(R)'l'i(N))
= ( 'l'f(N) Ittl Pkl'l'i(N)) <t/ltib(R)It/I~ib(R». (2.48)
28 2. Theory of Inner Shell Excitation Spectra

The squared overlap integral between the initial and final vibrational
wavefunctions

(2.49)

is the Franck-Condon factor which determines the intensities of the vibrational

peaks (Fig. 2.3). The intensities of electronic transitions shown between the
Vi = 0 electronic and vibrational ground state and the vibrational states vf of the
excited electronic state are determined by the overlap integral (2.49) over the
range of internuclear distances of Vi = O. We shall see below that in X-ray
absorption only resonances arising from bound state transitions are sufficiently
narrow that vibrational splittings may be resolved. The effect of the interplay
between the core hole lifetime and the vibrational time period for the correct
description of vibrational effects in core excited spectra is still the subject of
discussion in the literature [2.66-68]. In the following discussion of the dipole
matrix element Dif' we shall not continue to write down the vibrational overlap
term but it is understood that the full matrix element D!!;b defined by (2.48) does
contain such a term.

2.5.3 The Sudden Approximation

A great simplification in the calculation of the matrix element is achieved by a
fundamental assumption, known as the sudden approximation. Its essence lies in
assuming a strongly "one-electron" character of the electronic transition and
that the primary excitation event is rapid or "sudden" with respect to the
relaxation times of the other "passive" electrons. This allows separation of
the initial and final state wavefunctions into an "active" one-electron and a
"passive" multi-electron part, and the transition matrix element becomes

Dif = ( IJ'f(N) I kt1 Pk IlJ'i(N) )

= <xf lp114>1><lJ'f(N - 1)llJ'i(N - 1» + .... (2.50)

Here 4>1 is the orbital from which an electron is excited, Xf the wavefunction
of the excited electron, and the functions lJ'i(N - 1) and IJ'f(N - 1) are the
passive N - 1 electron remainders in the initial and final states. They are
(N - I)-dimensional Slater determinants in which one row and column corres-
ponding to 4>1 or Xf have been deleted [2.41]. In (2.50) we have omitted higher-
order terms which are associated with excitations of one or more of the "passive"
electrons [2.41]. In the sudden approximation we thus obtain as the leading
term a one-electron matrix element and an overlap integral between the passive
(N - I)-electron wavefunctions in the initial and final states. For the overlap
integral to be nonzero, the two functions lJ'i(N - 1) and IJ'f(N - 1) must
correspond to the same atomic symmetry or irreducible representation of the
symmetry point group of the molecule, the so-called monopole selection rule. The
 2.5 Transition Intensities 29

overlap term is always less than but close to 1 ( ~ 0.7-0.9) [2.69] and reflects the
intensity lost from the "main" one-electron transition by multi-electron effects.
Details of the various multi-electron excitation mechanisms and intensities
are contained in the higher-order terms omitted from (2.50). The form of this
equation suggests that there is a sum rule for the balance of the "one-electron"
and "multi-electron" intensities in the sudden approximation. The sum rule
states that the sum of the one- and multi-electron peak intensities for a given initial
state is equal to the peak intensity calculated by use of an unrelaxed final state
wavefunction. In the latter the matrix element stems from omission of the
passive-electron terms in (2.50), viz.

(2.51)

where the momentum operator is associated with the "active" electron. The
cross sections calculated using (2.51), called the active electron approximation,
are larger than those obtained in photoemission spectroscopy from the "main
peak" intensity alone, neglecting the satellite intensities [2.70].
In X-ray absorption spectroscopy two cases need to be distinguished. If only
the average cross section is of interest, e.g., all resonance effects are eliminated by
a smoothing procedure, then the measured cross section is well predicted by the
one-electron unrelaxed cross section since the measurement inherently sums
over all one- and multi-electron excitations. On the other hand, near edge
resonances or the EXAFS structure [2.71] are reduced in size by multi-electron
effects, similar to photoemission. The reason is that only those photoelectrons
which correspond to the "main peak" in photoemission are coherent and
therefore give rise to scattering resonances, while the electrons created in multi-
electron events are incoherent because of their smeared energy distribution.
A second sum rule, derived by Manne and Aberg [2.72], should also be
mentioned, and is best thought of in conjunction with core-level photoemission
spectra. In Koopmans' approximation all multi-electron effects are ignored and
the dipole matrix element describing the excitation of an electron in orbital 4Ji
has the simplest possible form given by (2.51). In this case a single photoemission
peak is observed corresponding to a binding energy Eb(i) = - E i • If we allow
passive electrons to relax and additional multi-electron excitations to occur, the
photoemission spectrum will exhibit a main "one-electron" line at a lower
binding energy Eb(i) = - E; - ..[Link] and higher binding energy multi-electron
satellites, i.e., shake-up and shake-off features. The sum rule states that there
exists a "lever arm" relationship between the one- and multi-electron peaks such
that the center of gravity of all photoemissionfeatures is at the Koopmans' binding
energy.

2.5.4 Adiabatic Versus Sudden Excitation

Qualification of the applicability of the sudden approximation in X-ray absorp-
tion is necessary. X-ray photoemission and EXAFS typically employ excitation
energies well above the IPs of the core electrons of interest and therefore the
30 2. Theory of Inner Shell Excitation Spectra

sudden approximation is justified. In near edge X-ray absorption spectroscopy,

the excited electron is either trapped in a bound state or leaves the atom or
molecule slowly. The appropriate physical picture, at least for transition ener-
gies close to the IP, is that the excited atom lowers its energy by slowly adjusting
to the effective atomic potential in an instantaneous, self-consistent way, the so-
called adiabatic excitation limit. The multi-electron statellites do not exist or are
of reduced intensity. In contrast to the second sum rule given above, which is
only valid in the sudden limit, the measured binding energy of the "main line" is
shifted from Koopman's value by a relaxation correction but "lever arm" multi-
electron intensities are absent.
Thus we have the remarkable situation that the IP measured in the sudden
limit by X-ray photoemission, i.e., the binding energy of the "main line", is identical
to the IP measured in the adiabatic limit by X-ray absorption, i.e., the position of
the "absorption edge". This has been carefully checked by comparing IPs
measured by photoemission with ISEELS results [2.73, 74], where the IP was
obtained by extrapolation of the Rydberg structures to an "absorption edge",
indicating the continuum onset as shown in Fig. 2.1. Further independent proof
is provided by zero kinetic energy electron spectra [2.75, 76] recorded with
tuneable synchrotron radiation where the IP in the adiabatic limit is directly
revealed as a pronounced peak.
To date the transition from "adiabatic" to "sudden" excitation is still not
well understood but it has been observed that satellite intensities are already
significant close to threshold [2.75-79] and the sudden limit appears to be
reached relatively fast, approximately within the first 10eV above the IP [2.77,
80,81]. Hence, in near edge X-ray absorption spectra multi-electron structures
are absent below the IP but they may be present above the IP, similar to
photoemission.

2.6 Bound Versus Continuum Final States

2.6.1 Improved Virtual Orbitals

For the calculation of K-shell spectra it is necessary to utilize techniques which
can account for transitions to bound and continuum final states. The energies
and wavefunctions describing the filled molecular orbitals of the N-electron
ground state of the molecule are obtained by solving the Hartree-Fock or
Roothaan-Hall HF equations as discussed earlier. Although solutions are also
obtained for empty or virtual orbitals, these do not represent an accurate
description of the excited or final state orbitals which are of interest in electronic
excitations. The final state of an electronic transition is described by the removal
of an electron from an inner orbital fjJi and addition of this electron to an outer
orbital fjJ f. In principle, the orbital fjJ f and its eigenvalue Ef should therefore be
obtained from a separate calculation for the excited electronic configuration. In
practice, this requires a new calculation for each final state fjJ f' a rather
 2.6 Bound Versus Continuum Final States 31

cumbersome task, and it is therefore common to use an approximate procedure

suggested by Hunt and Goddard [2.82]. In this method one neglects the
contribution of the excited outer shell electron to the molecular potential which
is then simply given by that of the ion, i.e., the (N - I)-electron system with an
electron missing in orbital41i. The Fock operator, see (2.25), in this, the so-called
static exchange, approximation is given by

(2.52)

where the summation is over doubly occupied orbitals "'k' not the previously
used singly occupied spin-orbitals 41k = "'kak (a k = ± 1/2). In deriving (2.52) we
have also made the restricted-Hartree-Fock assumption that all doubly occu-
pied orbitals are identical in their space parts such that there are exactly twice as
many nonzero Coulomb as exchange integrals. The orbital "'iis only singly
occupied and the sign of the exchange term depends on the singlet ( + K i ) or
triplet (- K i ) nature of the excited state. The empty orbitals '"f obtained as
solutions of F ex are commonly referred to as improved virtual orbitals and closely
correspond to the optical orbitals referred to in the experimental spectroscopy
literature.
Improved virtual orbitals have lower orbital energies compared to the
virtual orbitals obtained by Hartree-Fock ground state calculations (Sect. 2.1.1),
resulting from the additional Coulomb attraction of the excited (N - 1)-
compared to the ground-state N-electron system. Thus "unbound" virtual
orbitals with positive energy may correspond to "bound", negative-energy,
improved virtual orbitals. Note that excited electronic states may also be
described by the equivalent core model mentioned earlier, where the excited
atom with atomic number Z is replaced by a Z + 1 atom [2.63, 83, 84]. It should
also be noted that, in practice, the downward shift of the ground state virtual
orbitals caused by the core hole is often similar for the various orbitals such that
the relative ordering and intensities predicted by a ground state calculation may
be rather accurate.
By use of the ground-state Is core orbital and excited-state improved virtual
orbitals, it is straightforward to calculate the oscillator strengths or cross
sections of the discrete transitions according to (2.13) and (2.14). Such calcu-
lations may furthermore be carried out with great accuracy by using determin-
antal initial state and final state wavefunctions in the evaluation of the dipole
matrix element (2.47), or even include the effects of configuration interactions
[2.63,85].

2.6.2 Continuum Final States

In comparison, the calculation of the continuum cross section for molecules is
more difficult. At first sight this is not apparent since, in principle, virtual or
improved virtual orbitals with positive energy could be used, i.e., states which
32 2. Theory of Inner Shell Excitation Spectra

Orbital
Energy (eV)
co
15
..-,
"-;',
~, ~
N
'.
-~ '
3u~

, 10

5
2"'

50'

1"

40' ,.'-., Q.
t:,·_· c~~
':~,. :,;/

- 30

-35

30'

-45
Fig.2.S. Correlation between orbital energies and molecular orbitals for N2 and CO. The energies
of the filled and empty (indicated by an asterisk) orbitals are taken from Roothaan-Hall,
Hartree-Fock self-consistent field calculations with a Gaussian double-zeta basis set by Snyder and
Basch [2.36] ; the molecular orbital contour plots are taken from semiempirical calculations by
Jorgensen and Salem [2,86]

energetically overlap with the continuum of states above the vacuum level.
Examples are given in Fig. 2.5 for the simple diatomic molecules N 2 and CO,
where the orbital energies have been taken from Snyder and Basch's book
Molecular Wave Functions and Properties [2.36] and the orbital contours from
Jorgensen and Salem's The Organic Chemists Book of Orbitals [2.86]. Thus for
the two pictured cases one would expect resonances in the K-shell excitation
spectra corresponding to transitions to the virtual In: and 30': orbitals for N2
and the 2n* and 60'* orbitals for CO.
We have already encountered the 20' ---t 2n* excitation for CO in Fig. 2.4 and
have seen that for the core excited molecule the 2n * orbital is lowered below the
vacuum level, resulting in a bound state transition. On the other hand, we shall
 2.6 Bound Versus Continuum Final States 33

see below that the 1s -+ 60'* and 1s -+ 30': transition energies exceed the IP and
the corresponding resonances lie in the continuum. While MOs are useful in
visualizing transitions to quasi-bound resonant states embedded in the con-
tinuum, they do not represent a proper description of a continuum state suitable
for a cross section calculation. There are several reasons for this inadequacy.
First, the orbitals obtained from conventional bound state calculations obey the
orthonormality condition
(2.53)

while proper continuum or ionization states satisfy a Dirac delta-function

orthonormality in the kinetic energy E of the photoelectron [2.6], viz.,

(2.54)

Secondly, bound state and continuum functions satisfy different boundary

conditions in the asymptotic limit r -+ 00, where continuum functions approach
nearly pure plane wave character [2.87]. Finally, bound state functions cannot
account for the infinite degeneracy of the continuum at any energy E. Therefore
(improved) virtual orbitals do not provide stable and reliable solutions at
positive energies, and cannot be used without further development for the
calculation of ionization cross sections.
The difficulty in properly describing the continuum wavefunction of the
photoelectron for molecules lies in the nonlocal and noncentral nature of the
potential of the parent molecular ion. Ideally, one would use scattering theory
with appropriate boundary conditions and partial wave expansion techniques
[2.88] for the description of the motion of a low energy unbound electron in a
realistic potential of the molecular ion, but this approach has been impeded by
computational difficulties. For small molecules, progress has been made recently
in the construction of one-electron continuum functions which are solutions of
the static-exchange Hartree-Fock equation, fulfilling the proper normalization
and asymptotic boundary conditions for a free photoelectron [2.89]. Although
this technique may, in fact, be the technique of choice in the future we give brief
mention to it here.
Below we shall discuss two other techniques which have been extensively
used in the past for the calculation of K-shell spectra; much of our understand-
ing of the spectra is based on the results obtained with these techniques. The
first, so-called XtX multiple scattering (MS) method, [2.90,91] uses a simplific-
ation of the molecular potential, the so-called "muffin-tin" form, such that the
final state can be treated by customary partial wave expansions of scattering
theory [2.88]. The second, so-called Stieltjes-Tchebycheff (ST) moment theory
method, is based on first-principles molecular calculations. It constructs the
ionization cross section, using the theory of moments, from a large but finite
basis of eigenfunctions obtained by conventional Roothaan-Hall HF bound
state methods [2.92]. Below we shall outline the two approaches.
34 2. Theory of Inner Shell Excitation Spectra

2.7 The X~ Multiple Scattering Method

2.7.1 Introduction to the Method

The self-consistent field Xa-MS method, developed by Slater [2.46] and Johnson
[2.47] in the late 1960s, has been employed successfully for the calculation of the
electronic structure of molecules and clusters [2.48, 93-97]. The method is
capable of performing calculations for relatively large clusters (~50 atoms) by
employing two basic approximations: (i) the exchange potential in the
Hartree-Fock Hamiltonian is approximated by an average potential, deter-
mined by the total charge density, and (ii) the overall cluster potential is
approximated by a muffin-tin form. For this simplified form of the potential the
wavefunctions can be joined continuously throughout the various regions of the
cluster via multiply-scattered-wave theory (hence the name "multiple
scattering"). Originally the technique was used for bound electronic states but
following an early suggestion by Johnson [2.98] the method was extended by
Dill and Dehmer [2.99] and Davenport [2.91] in the mid 1970s to the description
of continuum final states, i.e., excited electronic states characterized by the
motion of a free photolectron in the field of an atomic or molecular ion.

2.7.2 Exchange Potential and Latter Tail

Let us briefly discuss the different steps carried out in Xa-MS calculations. First,
the one-electron Schr6dinger equation is solved for each individual atom or ion
which is part of the cluster. The calculation of the numerous two-electron
integrals is avoided by expressing both the Coulomb and exchange potentials
directly in terms of the total charge density of the other electrons. For the
Coulomb term this is straightforward but it is more difficult for the exchange
term. Following a density functional formalism introduced by Slater [2.30],
Gaspar [2.100], and Kohn and Sham [2.101], the exchange term given by (2.27)
can be written in the so-called "X a" form,
N
L Kkllp;(r»
k=l
= Vxa(r)llp;(r» . (2.55)

The exchange potential is given by

(2.56)

where
N
Q(r) = L nk¢t(r)¢k(r) (2.57)
k=l

is the local electron density (both spins) and {nd represents the occupation
 2.7 The XQ( Multiple Scattering Method 35

numbers of the various orbitals. The parameter IX is chosen on the basis of

atomic calculations by Schwarz [2.102]. Since IX is found to be close to 0.7 for all
but the lightest atoms, sometimes IX =0.7 is used for all atoms. In practice, the
charge densities calculated by Herman and Skillman [2.42], who used IX = 1, are
taken as the initial estimate for an atomic self-consistent-field calculation with
Schwarz's value of IX.
The failure of the XIX potential to correctly describe the Coulomb attraction
between the electron at large distance and the positive ion is sometimes
amended by applying a "Latter tail" correction [2.103]. This is simply done by
substituting the Coulomb potential e2 /r between the excited electron and the
positive molecular ion for the calculated potential VIII (see below) when the
magnitude of the latter drops below that of the Coulomb potential. Other forms
of the exchange potential can also be used, like the Hara exchange [2.104] which
is based on the free electron gas approximation [2.105]. Further refinements
include many-body effects, as in the complex Hedin-Lunqvist [2.106, 107]
exchange potential.

2.7.3 Muffin Tin Potential

In the second step the cluster is divided into regions as illustrated for a simple
diatomic molecule in Fig. 2.6. Each atom is first surrounded by a sphere with
radius bi and then the entire cluster is surrounded in a close-packed fashion by
an outer sphere with radius bo centered on the molecular center of mass and
creating regions Ii' II and III, respectively. The potential at an arbitrary point r
is then obtained as a superposition of the individual potentials of the atoms
centered at positions R i ,

V(r) = L V~(ri) + V~<z(rJ .

i
(2.58)

Here we have explicitly indicated that the local potentials are a sum of the
total (electron-nuclear plus electron--electron) Coulomb potential V~(ri) and
exchange potential V~ (rJ [compare (2.25) and (2.44)], and we have defined

Fig. 2.6. Partitioning of the molecular field for a hetero-

nuclear diatomic molecule. The corresponding muffin-tin
potential is spherically symmetric in regions 11 ,1 2 and III
and constant in region II. The coordinate vectors'l and'2
'j
are centered on the atoms, while, = R j + is centered on
the molecular center of gravity. IRti + IR21 is the inter-
nuclear distance
36 2. Theory of Inner Shell Excitation Spectra

r i = r - Ri (Fig. 2.6). The potentials in regions Ii are then expressed as an

expansion of V(r) in a series of spherical harmonics, using theorems described
by Liiwdin [2.108]. By retaining only the first (l = m = 0) spherically symmetric
term V'(r;) in regions Ii' the potential assumes a "muffin-tin" form. In region II
the potential is averaged to a constant value, often referred to as the "inner
potential" in the literature. In region III a spherical average is taken with respect
to the center of the molecule, resulting in the potential VIII (r).
The relative sphere radii around the atoms, i.e., their ratios, are typically
chosen, following a suggestion by Norman [2.109], to be proportional to the
volumes containing the atomic number of electrons. With the ratio of radii fixed,
the spheres around individual atoms are chosen to minimize the region II
between the spheres where the potential is least well defined. Often the spheres
are made to touch but they may be chosen to overlap. Wurth and Stohr [2.53]
have suggested that for the calculation of K-shell spectra the overlap may be
chosen in a semiempirical fashion. By performing a transition state calculation
with half an electron removed from the Is shell the overlap is adjusted such that
the calculated Is "orbital energy" relative to the vacuum level matches the
experimental IP.

2.7.4 Multiple Scattering Wavefunctions

In the third step the wavefunctions are constructed. In region Ii single

center wavefunctions are written in terms of solutions RI(E, ri) of the radial
Schrodinger equation with the potential V'(r i ), real spherical harmonics Yi(ri),
and to-be-determined partial wave coefficients cl. m according to

I/I(ri) = L CLmR,(E,ri ) Yi(r i ) .

I.m
(2.59)

To speed up the molecular calculation, symmetry adapted functions are used.

The functions are chosen such that they form a basis for one of the irreducible
representations of the molecular point group, either the nuclear point group
symmetry or a broken symmetry, e.g., assuming a localized core hole. In
practice, a computer program by Cook [2.110] can be used which determines the
appropriate basis functions automatically, with only the molecular geometry as
input.
The wavefunctions in region III also have the form given by (2.59) but are
centered on the molecular center and use radial functions which are solutions of
the SchrOdinger equation with the potential VIII(r). In region II a multicenter
partial-wave representation is used where the radial functions are expressed in
terms of spherical Bessel, Hankel and Neuman functions about the molecular
center and the atomic positions [2.47].
By use of expansion theorems the multicenter wavefunctions can be re-
written in terms of single-center wavefunctions around the molecular center and
distances between the centers. Because there must be outer sphere basis func-
 2.7 The XC( Multiple Scattering Method 37

tions for every irreducible representation the maximum angular momentum

quantum number, I, should be greater in the outer sphere region than on the
atomic centers. All regional wavefunctions and their derivatives are required to
be continuous at all spherical boundaries. These boundary conditions allow
mapping of a given partial wave near an atomic nucleus into the asymptotic
partial waves in region III [2.48] and lead to explicit relations between partial-
wave coefficients. These relations may be written as linear homogeneous equa-
tions which constitute the secular equations of the Xa-MS method.
In discussing the results from Xa-MS calculations it is important to dis-
tinguish between the local angular momentum states around an atom (region I)
and the partial wave label in the asymptotic molecular wavefunction (region III).
In X-ray absorption from a given initial state only those final states are allowed
in the "atomic-like" environment of the local region I which obey the dipole
selection rule ~I = ± 1, i.e., for an s initial state only the p-wave component of
the final state is allowed. On leaving the excited atom in region I the photo-
electron is scattered by the anisotropic molecular potential into the entire range
of angular momentum states contributing to a given, e.g., the (J, ionization
channel. The resonances calculated by MS theory are typically discussed in
terms of specific resonating 1channels which are the asymptotic labels in region
III, i.e., the corresponding wavefunctions are expanded about the center of the
molecule.
Of special importance for the understanding of the scattering processes are
the so-called eigenchannel wavefunctions obtained by diagonalizing the K -matrix
[2.99, 111, 112]. The partial-wave character of these functions remains un-
changed by scattering processes in the molecular potential and they can there-
fore be used to represent the final state in a manner similar to contour plots used
in conjunction with molecular orbitals [2.112]. These concepts will be discussed
in more detail for the N2 K-shell spectrum in Section 4.2.6.

2.7.5 Transition Energies

The orbital energies are obtained by finding the zeros of a secular determinant
[2.48]. Since the elements of the determinant contain the energy as a parameter
one must calculate the value of the determinant for a series of closely spaced
energies and ascertain where it changes sign. For core states the determination
of the orbital energies is simplified significantly by limiting the potential to the
appropriate atomic sphere. To obtain ionization potentials of resonable accur-
acy the transition state method discussed in Sect. 2.4.2 is used. The excitation
energy for a given electronic transition is obtained from a calculation in which
half an electron is removed from the K-shell. In principle, for bound-state
transitions half an electron should be added to the unoccupied orbital, with the
transition energy being the difference in orbital energies of the fractionally
occupied orbitals. However, this scheme requires a new calculation for every
excited state. In practice, the virtual orbitals may be left unoccupied since this
does not affect the transition energies significantly, as discussed in Sect. 2.4.2.
38 2. Theory of Inner Shell Excitation Spectra

2.7.6 Practical Procedures for Calculation of K-Shell Spectra

The set of wavefunctions obtained for the occupied orbitals after the first pass
leads to an electronic charge density from which a new potential of the form
given by (2.58) is generated. This potential is spherically averaged in regions Ii
and III and volume-averaged to a constant value in region II. An iteration is
then started by using a suitable combination of this new potential and the
original one to calculate new wavefunctions and eigenvalues. The entire nu-
merical procedure is repeated until self-consistency of the charge densities and
potentials is achieved.
In Fig. 2.7 is plotted the fully converged self-consistent potential V(r), (2.58),
calculated for the N 2 molecule in its electronic ground state under the assump-
tion of touching muffin-tin spheres. The potential is plotted along the inter-
nuclear axis and includes the nuclear positions. Note that the potential is
discontinuous at the sphere boundaries. We have also indicated the value
(-28.1 eV) of the "inner potential" VII. The small kink in the potential near Irl
= 1.3 A arises from attaching the "Latter tail" Coulomb potential at this point.
It can be seen that the "Latter tail" falls off more gradually with Irl than the
extrapolated XIX potential. Above we have deliberately used the symbollrl for
the distance from the molecular center to make clear that Irl is not a spherical
coordinate. If expressed in the spherical coordinate r the potential would look
quite different and contain a potential barrier arising from the centrifugal
potential term h2l (l + 1)/(2mr2) as discussed in Sect. 4.2.1. The sensitivity of the
calculated K-shell spectrum to the choice of the potential will be discussed in
Sect. 4.2.6.

Xa Potential for N2

III Fig. 2.7. Construction of muffin-tin

spheres and resulting self-consistent mo-
lecular potential for N 2' (2.58), as a func-
I tion of the distance Irl from the center of
I
I the molecule, calculated by the XIX-MS
Latter tail - I I 1 - Latter tail technique. The potential is plotted along
o I I I the internuclear axis, and as shown in the
I I I top part of the figure we have chosen
I
> -20 __ y:~_ I _J __: touching spheres with a radius around the
atomic centers of 0,55 A and an outer
~ I
,-: -40 I sphere radius around the molecular center
>" I
I
of 1.l0A. We have used maximum angular
iii momenta of Imax = 4 relative to the atomic
E., -60 I
centers and Imax = 7 relative to the center of
I
(5
Cl. I the molecule. The inner potential VII is
-80 I
I
calculated to be -[Link], The change of
the potential near Irl = 1.3 A is associated
- 100 '---:_2:-..J....-_~1_,,-I~~-"-~--'---2=----'

Distance from Molecular Center, r" (AI

with the "Latter tail" which is substituted
for the XIX potential at larger distances
 2.8 Ab Initio Stieltjes-Tchebycheff Molecular Orbital Method 39

The X-ray absorption cross section is calculated according to (2.8) and (2.14)
by use of the XIX-MS wavefunctions for continuum and bound states, respect-
ively. Rather than using the momentum operator form of (2.8), in practice, the
acceleration form given by (2.11) is used, as suggested by Davenport [2.113] and
Noodleman [2.114]. This has the advantage that VV = 0 in the interstitial region
II and the matrix element is simply the sum of terms over the atomic and outer
sphere regions. Bound-state transitions which occur at discrete energies and
transitions to continuum states require separate calculations but they can be
joined continuously by utilizing (2.14).
In this volume many calculated K-shell spectra will be presented. The
following computational strategy was used. (1) A broken molecular symmetry is
employed with half an electron in the Is orbital of a particular atom of the
molecule. (2) The sphere overlap is chosen such that the Is orbital energy
calculated by the transition state method matches the experimental IP. (3) The
same transition state potential is used for bound and continuum states. (4) The
calculated bound state oscillator strength is converted into a cross section by use
of (2.14). A Gaussian (Lorentzian) line shape function is used whose width
represents the instrumental (lifetime) resolution and whose area is the oscillator
strength. (5) The calculated continuum cross section is convoluted with the same
Gaussian or Lorentzian function used for the discrete part of the spectrum.
To date the XIX-MS method has been extensively applied to the calculation of
K-shell excitation spectra of simple and complex molecules and several reviews
of the technique itself [2.111,115] and the results obtained [2.53,96,97,116] are
available.

2.8 Ab Initio Stieltjes-Tchebycheff Molecular Orbital Method

2.8.1 Introduction to the Method

The second theoretical method used for the description of K -shell spectra of
molecules, developed by Langhoff et al. [2.92, 117-120], uses the concepts of
valence molecular orbitals (MOs), developed by Mulliken [2.121], and conven-
tional Roothaan-Hall HF computational techniques. By use of the Stieltjes-
Tchebycheff moment-theory techniques the continuum cross section is obtained
by smoothing discrete cross sections calculated by use of a finite number of
ground state and excited state MOs. This technique thus uses a highly accurate
molecular potential, in contrast to the XIX-MS technique, but avoids the difficult-
ies associated with the construction of proper continuum functions by use of
improved virtual orbitals and a smoothing procedure.

2.8.2 Calculational Procedure

Calculations begin by solving the Hartree-Fock equations for the ground state
electronic configuration. The resulting canonical Fock orbitals are then used to
40 2. Theory of Inner Shell Excitation Spectra

construct the Fock operator in the static exchange form (2.52), appropriate for
excitation of an electron from a selected orbital o/i' The two calculations yield
the eigenvalue Ei and eigenfunction o/i of the initial state orbital of the active
electron and M improved virtual orbitals 0/ j and the corresponding negative
(bound) and positive ("unbound") energies E j ' Typically, in the binding energy
calculation of the core state, relaxation is not explicitly included but is allowed
for by using experimentally determined 1s IPs rather than Koopmans' eigen-
values E i •
Since a fairly extended array of virtual orbitals is required to account for the
densely spaced Rydberg orbitals and the "unbound" orbitals above the vacuum
level, a large set of compact and diffuse basis functions is chosen for expansion of
the improved virtual orbitals while the occupied orbitals are described by a
modest number of valence-like basis functions. The set of M improved virtual
orbitals which are chosen to be Lebesgue square-integrable (so-called L 2 )
eigenfunctions and their eigenvalues form a pseudo-spectrum {o/ j' E j;
f = 1, ... ,M} from which discrete cross section values, compare (2.8, 14), can
be calculated according to

(2.60)

where hW ij = Ej - E i .
The pseudo spectrum identifies physically distinct final states which are
expected to dominate the photoabsorption cross section. It is evident, however,
that the wavefunctions do not satisfy the normalization and asymptotic bound-
ary condition of proper continuum states. Although, in general, the improved
virtual orbitals comprising the pseudo spectrum can be obtained by some linear
combination of continuum functions, it is not necessary to explicitly specify the
continuum functions in computing reliable ionization cress sections. Instead,
they are obtained by smoothing the discrete cross sections given by (2.60) by use
of theorems from the theory of moments [2.122, 123]. According to one theorem
the cross section is uniquely determined by its spectral moments,

J(hw)-kaAhw)d(hw) .
00

11k = (2.61)
IP

It is found that for a sufficiently large number M of improved virtual orbitals

the moments of(2.61) for k:::5 M/2 can be approximated by those obtained from
the discrete cross section according to

(2.62)

The Stieltjes-Tchebycheff approach is then used for the construction of the

ionization cross section from a finite number of moments. In principle, this
 2.8 Ab Initio Stieltjes-Tchebycheff Molecular Orbital Method 41

method corresponds to a finite-energy-interval averaging of the pseudospectrum

but in contrast to step-like "bin-smoothing" it produces a smooth oscillator
strength density with resonance-like structures at the appropriate discrete
transition energies. For a detailed discussion of the technique the reader is
referred to reviews by Langhoff [2.118-120].

2.8.3 Stieltjes-Tchebychelf Orbitals

Because the ST-MO technique uses improved virtual orbitals for the construc-
tion of the ionization cross section it is not surprising that the technique
identifies particular virtual orbitals that are associated with strong continuum
resonances. The orbital nature of continuum scattering functions is most
elegantly established by pictorial examination of so-called "dipole interaction
prepared states" or Stieltjes-Tchebycheff orbitals [2.120, 124-126], which allow
convenient graphical illustrations similar to bound state orbitals. The ST
orbitals closely correspond to the eigenchannel wavefunctions discussed earlier
in the context of XIX-MS calculations. They are constructed to specifically
identify the resonant channels in the eigenchannel functions, thus avoiding the
explicit construction of all the degenerate eigenchannel solutions, i.e., of the
entire spectrum of continuum functions. Note that these functions are construc-
ted by using the cross section as a normalization factor, and therefore this
procedure does not provide an alternative method for the construction of the
cross section itself.
Figure 2.8 compares the outer MOs of nitric oxide (NO) calculated by the
Hartree-Fock method in a minimal Gaussian basis set [2.119] with the ST
orbitals corresponding to ionization of the 50" MO at various excitation energies
e. At e = 25.2eV the ST orbital reveals a remarkable similarity (except for an
arbitrary phase reversal) to the empty 60"* MO obtained with the HF minimal
basis set calculation, indicating that the resonance observed experimentally at
this excitation energy [2.127, 128] arises from a 60"* orbital embedded in the
continuum. Note that the difference in orbital energies between the 50" and 60"*
orbitals of 39.2eV, corresponding to the 50" --+ 60"* transition energy, obtained
with the ground state HF calculation is much greater due to the neglect of final
state relaxation than the resonant excitation energy of ~ 25 eV obtained with
the static exchange Hamiltonian used for the ST calculation.
The connection between continuum shape resonances and minimal basis
set MOs has also been examined by Thiel et al. [2.129, 130] who suggested that
one may view this resonance as a two-step, one-electron process where a K-shell
electron is excited to an unoccupied virtual orbital of 0" symmetry and then
decays into the continuum as a photoelectron. The unified description of bound
state and continuum resonances as transitions to well-defined molecular final
states emerging from ST-MO calculations has many virtues for our understand-
ing of the overall characteristics of K-shell excitation spectra, and we shall use
this concept throughout.
42 2. Theory of Inner Shell Excitation Spectra

Minimal Basis set MO's 5a-Ea Stieltjes Orbitals

NO

Fig. 2.8. On the left are shown molecular orbitals for NO constructed in a minimal Cartesian
Gaussian basis set [2.119, 126). Calculated orbital energies are also shown. The orbitals are plotted
in a 3.2 A x 8.5 A plane that includes the internuclear axis, with N on the left and 0 on the right. The
6cr* orbital is empty, the 2n* orbital filled with only one electron and all other orbitals are occupied.
On the right are shown Stieltjes orbitals and excitation energies appropriate for 5cr -+ ecr ionization
of NO. The Stieltjes orbitals represent the scattering functions of an electron excited from the 5cr
orbital, shown at the bottom, with a binding energy of 16.5 eV. At an excitation energy of about
25 eV, corresponding to a resonance energy of about 8.5 eV above the vacuum level, the Stieltjes
orbital reveals a remarkable similarity, except for an arbitrary phase change, to the 6cr* orbital
(dashed arrow)

2.8.4 Feshbach-Fano Method

Finally we briefly mention the development of a new but related method
of calculating resonant molecular continuum cross sections, developed by
Winstead and Langhoff [2.131, 132J and reviewed by Gil et al. [2.133]. This
method uses the fact that, in many cases, continuum resonances can be under-
stood as arising from the interaction of a discrete state with nonresonant
 2.9 Shell-by-Shell Multiple Scattering Method 43

continuum channels, as originally pointed out by Feshbach [2.134] and Fano

and Cooper [2.10, 135]. The Feshbach-Fano method yields a convenient
parameterization of the photoionization cross section profile, the parameters
being (1) a nonresonant background cross section, expressed as the square of a
dipole matrix element between the initial core state and degenerate background
scattering states, (2) an overlap parameter, which characterizes the interaction of
the discrete state with the degenerate background scattering states, and (3) a
strongly energy dependent profile junction, dependent on energy-width and
energy-shift functions. This method is readily adapted to the quantitative
calculation of molecular (1* resonance cross sections by use of minimal basis
set (1* orbitals for the "discrete state(s)") and approximating the "background
states" by linear combinations of a large but finite number of L 2 wavefunctions
[2.131, 132, 136]. The success of such calculations underlines the relevance of
minimum basis set MOs to the understanding of (1* continuum resonances.

2.9 Shell-by-Shell Multiple Scattering Method

We briefly discuss below a third method that has been employed for the
calculation of near edge spectra of various solids, molecular complexes, and for
chemisorbed atoms on surfaces. Since the method has been reviewed in detail
elsewhere [2.137] and because of its limited applicability for the calculation of
NEXAFS spectra of chemisorbed molecules, a rather short account will be
given.
The particular multiple scattering method of interest was introduced by
Durham et al. in 1981 [2.138, 139] and is formulated in a real-space cluster
model. The code was later updated with emphasis on surfaces by Vvedensky et
al. [2.140]. The essence of this theoretical approach is the exact formulation,
within the one-electron approximation, of the scattering process of the photo-
electron excited on the central atom by the surrounding neighbors with in-
finitely many scattering events (multiple scattering) included. These events may
not only occur in a back scattering geometry as in the EXAFS approximation
but at any angle, and thus the photoelectron wave may bounce off numerous
atoms before returning to the origin. Scattering is considered in a shell-by-shell
manner, where a "shell" consists of atoms which have similar but not necessarily
identical distances from the origin and may even contain different atoms. Both,
intra- and inter-shell scattering is taken into account. By adding shells, the
results may be checked for convergence with respect to the cluster size and large
clusters consisting of more than 50 atoms can be handled on a personal
computer.
The crucial part of the calculation is the construction of a realistic potential
which reflects not only the core but also the valence charge distribution. Since
the shape of the potential near the vacuum level, which is largely determined by
the valence electrons, greatly influences the scattering processes of a low-energy
44 2. Theory of Inner Shell Excitation Spectra

photoelectron, it is highly desirable to use self-consistent procedures for the

calculation of the potential. Unfortunately, at present, self-consistent calcu-
lations have not yet been carried out and the potentials for the adsorbate system
under investigation are typically constructed by using a "model compound",
either an adsorbate system or bulk compound of well-known structure con-
sisting of the same atomic species. For this model compound the potentials are
chosen such that the calculation accurately reflects the measured NEXAFS
spectrum.
Because of the lack of self-consistency, at present the method is deemed
of insufficient reliability for the calculation of K -shell spectra of free and chemi-
sorbed molecules. We shall, however, use results obtained with this method in
Sect. 6.2.1, in the discussion of the qualitative differences between the K-shell
excitation spectra of chemisorbed atoms and molecules.

2.10 Approximations Leading to the EXAFS Equation

During the last twenty years it has been not the near-edge but the extended X-ray
absorption fine structure, or EXAFS, that has received the most attention
[2.141]. The reason is the close and simple link between the EXAFS oscillations
and the local crystallographic structure about the central excited atom. Al-
though EXAFS is not the topic of this book, it is obviously closely linked with
NEXAFS in that the NEXAFS and EXAFS regions smoothly join together in
the range 30-50eV above the absorption edge. We therefore need to examine
how the scattering processes of the photoelectron change with increasing energy.
Also, in the high-excitation-energy region certain approximations can be made
which lead to an analytical expression for the EXAFS structure. The interested
reader is referred to Appendix A where the EXAFS equation is derived. In this
case, it is possible to follow all physical processes using relatively simple
mathematical concepts and the treatise in Appendix A greatly helps in under-
standing the scattered-wave or partial wave concepts outlined earlier in the
discussion of the XO(-MS technique.
Here we shall simply state the final result for the EXAFS equation and
discuss the link between the NEXAFS and EXAFS. The polarization dependent
EXAFS signal as a function of the photoelectron wavevector k is given by
(A.47). If we group all atoms j with the same atomic number Z around the
central excited atom into shells i of equal distance R i , then the EXAFS signal is
given by

3 cos 2 ()..
+ 215 1 + Pd.
2 2
x(k) = - ~ kR2 IJ F i (k)e- 2t1 ,k e- 2R .;).,(k)sin(2kR i (2.63)
.,] i

Here cos 2 (}ij is a polarization dependent factor, Fi(k) the back scattering ampli-
tude characteristic of a neighbor with atomic number Z, exp( - 2o} P) the
 2.10 Approximations Leading to the EXAFS Equation 45

Debye-Waller-like term accounting for thermal vibrations, exp[ - 2R;/A;(k)]

the term accounting for the finite inelastic mean free path of the photoelec-
tron, and the sinusoidal term contains the distance and scattering phaseshift
dependence.
Let us review the approximations and limitations of (2.63), ignoring the
vibrational and inelastic terms. Three fundamental approximations were made:
(1) Neglect of multiple scattering, (2) point scattering at the neighbor atom, and
(3) use of the asymptotic limit for spherical waves. We shall discuss these
approximations in turn.
As the kinetic energy of the excited photoelectron becomes large relative to
its interaction energy with the surrounding atoms (a few eV) the scattering by
the neighbor atoms is largely determined by their atomic-like core potentials.
We can then use the approximation that the scattering off the neighbors is a
simple sum of their isolated contributions. In this single scattering model,
multiple scattering between several centers is ignored, and all the physics is
contained in the proper description of the final state wavefunction for a
diatomic, as done in Appendix A. Larger systems can be treated using a building
block principle. The essence of the single scattering approximation therefore lies
in the fact that at sufficiently high photoelectron kinetic energy the scattering
processes off neighboring atoms are dominated by the core rather than the
valence electron potential, and the scattering cross sections are peaked in the
forward and backward directions [2.142]. For this reason scattering phaseshifts
in the EXAFS region can be derived from atomic potentials. The charge overlap
between bonded atoms is either ignored and retroactively incorporated into the
analysis by use of an adjustable inner potential [2.141], or in a better ap-
proximation [2.143, 144] is accounted for by use of a non-self-consistent muffin-
tin potential which allows the determination of the inner potential, i.e., the zero
of energy of the EXAFS scale.
Because all multiple scattering path lengths are substantially longer than the
single scattering path length to a nearest neighbor atom and back, multiple
scattering can be ignored in the EXAFS analysis of the nearest neighbor shell
structure. Bunker and Stern [2.145] have argued that multiple scattering is only
important in the EXAFS region if an intervening atom lies approximately
collinear with the central atom and the backscattering atom. In this case
forward scattering needs to be considered in addition to backscattering, and the
photoelectron wave may be focused by the intervening atom onto the next
nearest neighbor atom. A significant change in amplitude and phase of the
EXAFS signal may result [2.146]. Bunker and Stern pointed out that in
exceptional cases where the bond length becomes short ( < 1.6 A) and there is no
center of inversion symmetry, other types of multiple scattering effects could also
be important in the EXAFS region.
Evidence for large-angle multiple scattering events in the EXAFS region has
been found for low-Z atoms chemisorbed onto metal surfaces by Arvanitis et al.
[2.147]. In this case single scattering contributions from higher neighbor shells
are weak and large angle multiple scattering events within the first neighbor
46 2. Theory of Inner Shell Excitation Spectra

shell may be detected since they involve comparable path lengths and ampli-
tudes to the former. Thus care has to be exercised in the interpretation of all
peaks in the Fourier transform at distances larger than the dominant nearest
neighbor shell peak.
For low-Z molecules, multiple scattering within the molecule leads to large
resonances in the near-edge region. These resonances, which are the main topic
of this volume, can be thought of as a trapping of the photoelectron wave by the
molecular potential which is largely determined by the valence electron charge
distribution. In particular, the so-called a* shape resonances discussed in Sect.
4.2.4 may be understood as back and forth scattering of the photoelectron wave
between two atoms. Although the higher energy EXAFS oscillations have a
close connection to the a * resonance as discussed in Sect. 8.2, they can
nevertheless be accounted for by a single scattering theory [2.148]. One simply
needs to include curved wave effects and the charge overlap caused by the
intramolecular bonding, as in the theory of Rehr et al. [2.143, 144].
It is easy to understand why approximations (2) and (3), which formally lead
to the plane-wave limit [2.149-151], become better with increasing kinetic
energy of the photoelectron. The higher the kinetic energy, the more the
photoelectron will penetrate the core of the neighbor atom and the scattering
will be increasingly dominated by core electrons and the nuclear potential.
Hence point scattering becomes a better approximation. With increasing energy
and therefore wavevector k all mathematical expressionsf(kr) encountered in
the derivation in Appendix A become closer to their asymptotic kr -+ 00 value.
Thus, spherical waves, in general given by Hankel functions, approach their
asymptotic limit in the EXAFS range.
The two approximations (2) and (3) lead to two problems. First, as shown by
Schaich [2.152] and Gurman et al. [2.153], in a proper spherical wave treatment,
the EXAFS phase shifts and scattering amplitudes become dependent on the
bond length R. This can be seen from (A.30), which only in the asymptotic limit
can be factored into an r'-independent amplitude and phase scattering function.
In practice, the R-dependence is taken into account either by use of standards or
properly calculated phases and amplitudes [2.154, 155].
Second, one has to neglect a depolarization term [2.156, 157]. By neglecting
the finite size of the scattering center B, this term which is proportional to
e,
sin 2 is absent. The origin of the depolarization term is easy to understand.
Assume that the E vector is aligned perpendicular to the internuclear axis R of a
diatomic. The photoelectron dipole pattern on the excited atom A which is
directed along the E vector will then also be perpendicular to the internuclear
axis. Thus a point-like neighbor atom B will lie in the nodal plane of the dipole
pattern and no electrons can scatter off it. For a finite-sized atom (potential) at
B, however, photoelectrons which are emitted at finite angles with respect to the
internuclear axis can scatter off atom B and therefore produce EXAFS. The
depolarization term was first observed, but not specificallY identified, in the XIX-
MS calculation for the N2 molecule by Dehmer and Dill [2.B], who found
pronounced EXAFS oscillations in the 7t ionization channel, which by definition
 2.10 Approximations Leading to the EXAFS Equation 47

is the EXAFS contribution for E perpendicular to the internuclear axis. Al-

though this depolarization contribution will be small compared to the max-
imum contribution (the "(J contribution") when Ell R, it may nevertheless cause
problems in analyzing amplitude ratios [2.157] in polarization-dependent
SEXAFS studies [2.158].
It is interesting to note that the depolarization term is of fundamental
importance at low photoelectron energies, i.e., in the NEXAFS range. In this
case the low-energy electron can be effectively scattered by the molecular
potential, which is largely determined by the valence charge distribution, even
when emitted perpendicular to the internuclear axis, and pronounced reson-
ances, e.g., n* resonances, are observed. Since in NEXAFS the observed
resonances are associated with molecular orbitals of well-defined symmetry, the
contributions from final states of different symmetry are naturally isolated, as
long as the resonances are separated in energy.
3. Symmetry and Molecular Orbitals

In this chapter the rudiments of molecular orbital theory are reviewed in the
light of their importance for the understanding of the resonances which domin-
ate molecular X-ray absorption spectra. Particular emphasis is given to the
symmetry classification of orbitals and how it relates to the polarization
dependent dipole selection rule that governs X-ray absorption.

3.1 Origin and Labelling of Molecular Orbitals

Although the calculation of the detailed resonance positions and intensities of

molecular K-shell excitation spectra requires initial and final state wave-
functions obtained by solving the Schrodinger equation, there are some simple
symmetry classifications of resonances which arise from the one-to-one corres-
pondence between resonances and molecular orbitals. This symmetry labeling
not only facilitates the understanding of the K -shell spectra of free molecules
discussed in the following section but it is particularly useful in describing the
dependence of resonance intensities on X-ray polarization, as discussed in
Chap. 9.
The close correlation between K -shell resonances and specific molecular
orbital final states revealed by Stieltjes-Tchebycheff MO calculations [3.1-5J
makes it important to develop an understanding of MO concepts [3.6-12]. The
simplest symmetry classification for low-Z molecules is in terms of a and n
orbitals [3.8]. For K-shell excitations the initial Is state is always of.a symmetry
while the final states allowed by the dipole selection rule have to contain an
atomic p-orbital component, and may be of a or n symmetry. In this volume we
are mainly concerned with low-Z molecules, composed of the atoms H, C, N, 0
and F. Bonds between these atoms involve the Is electrons of H and/or the 2s
and 2p electrons of the second row atoms. The composition of the molecular
wavefunction is a linear combination of atomic orbitals (LCAO) according to
(2.34).
If for the description of diatomics we choose a coordinate system with its z-
axis along the internuclear axis, a valence orbitals originate from atomic 2s
and/or 2pz orbitals and n orbitals arise from 2px and 2py atomic orbitals [3.6, 8,
10]. According to perturbation theory the degree of mixing of the 2s and 2pz
orbitals depends on the energy separation of the 2s and 2p orbitals which
 3.2 Some Molecular Orbitals and Irreducible Representations 49

increases from about 2 eV in Li to about 22 eV in F, and therefore the mixing is

weaker in F 2 than N 2. In the presence of hydrogen bonds the H Is orbital may
mix, if allowed by symmetry, with the 2s and 2p orbitals of the second row
atoms. Important examples are hydrocarbons, in which bonding and anti-
bonding MOs are formed from the Is orbital of hydrogen (Eb(ls) = 1 Rydberg
or 13.6 eV) and the 2s and 2p orbitals of carbon (Eb(2p) ~ 14 eV and
Eb(2s) ~ 23 eV [3.13J).
For diatomics, a orbitals are symmetric with respect to reflection through a
plane containing the symmetry axis of the molecule and 1t orbitals are antisym-
metric. In poly atomic molecules, the molecular orbitals involve atomic overlap,
which is generally more extended, but the resulting orbitals can still be labeled
either a, symmetric, or 1t, antisymmetric, with respect to a local symmetry plane
[3.8]. For a orbitals or bonds there is no nodal surface that contains the bond
axis, while a 1t bond has one nodal surface or plane containing the bond axis.
The a bond is always present while the existence of a 1t bond depends on the
atomic constituents of the molecule and the number of valence electrons
available for bonding. The a and 1t manifolds each contain both bonding and
anti bonding orbitals corresponding to in-phase and out-of-phase orbital ampli-
tudes on adjacent, bonding atoms.
For K-shell spectra, it is the nonfilled antibonding orbitals which are of
importance, since the observed resonances correspond to dipole allowed trans-
itions of a Is core electron to 1t and a antibonding orbitals. For homonuclear
molecules, orbitals are given a second label g (gerade) or u (ungerade) indicating
the inversion symmetry through the center of the molecule. The wavefunction of
g orbitals is symmetric, that of u orbitals antisymmetric with respect to inver-
sion. For complex molecules it is appropriate to use group theory and designate
the MOs by their irreducible representations, rather than by the simple a and 1t
label [3.11, 14]. Below we shall meet examples of how MOs for molecules of
increasing complexity are constructed by the LCAO scheme under group-
theoretical symmetry constraints.

3.2 Some Molecular Orbitals and Irreducible Representations

3.2.1 Diatomics and Linear Triatomics

The simplest MOs are those of diatomic molecules. Figure 3.1 illustrates how
atomic orbitals combine to produce molecular orbitals using the diatomic
homonuclear N2 molecule as an example [3.10]. We again choose a coordinate
system with the z-axis pointing along the internuclear axis. If we ignore the
mixing of the 2s and 2pz atomic orbitals, the interaction of the 2pz atomic
orbitals on each N atom leads to a bonding (3ag ) and antibonding (3a u ) MO of a
symmetry. The 2px and 2py orbitals on each N atom form two orthogonal but
energetically equivalent 1t bonds characterized by the bonding (l1tu) and anti-
50 3. Symmetry and Molecular Orbitals

Atom 1 Molecule Atom 2 Fig. 3.1. Diagram of the formation of molecular

3<7 u orbitals from atomic orbitals in a homonuclear
diatomic molecule consisting of second row atoms
(i.e., Li2 through F2). The asymmetric spacing of
the four highest (J orbitals about the 2p and 2s
centers of gravity is due to a mixing of the 2s and
2pz atomic orbitals as discussed in the text. In
17T 9
~
particular, the shown order of the 311, and lnu

~~::5
x 2p .~'i'l'l 2p x orbitals reverses for molecules heavier than N2
y 3<79 Y [3.15]. Also the occupation changes across the
z ~*-'~ ..... Z
" ..:::::.~

17T u
/-:/
'l
series. For Li2 the 211u is the lowest unoccupied
MO, for N2 the In. orbital. Note in particular
25 ......... 25 that 02 has two electrons with parallel spins
2<7u
(Hund's rule) in the two In. orbitals and is there-
fore paramagnetic. (From [3.10])

2<79

1<7u
15 . . . . . . .. . ....... ::. 15
... .....
1<79

bonding (Ing) orbitals. Combination of the two 2s orbitals leads to a bonding

(20"g) and anti bonding (20"u) combination. Because the Is atomic orbitals are so
localized the lowest MO in N2 is a nearly degenerate 100g and 100u combination.
The bonding 0" orbitals are gerade with respect to inversion through the center of
the molecule and the antibonding 0" orbitals ungerade. For n orbitals the reverse
is true. Consideration of the mixing of the 2s and 2pz atomic orbitals leads to an
asymmetric spacing of the energy levels of 0" symmetry around their atomic
centers of gravity (Fig. 3.1), resulting from a repulsion between the mainly 2pz
and mainly 2s derived MOs, respectively. N2 is said to be triple bonded by one 0"
(the 20"g is the most strongly bonding MO) and two n bonds.
The schematic energy level diagram shown in Fig. 3.1 describes the bonding
of molecules ranging from Li2 to F 2' With increasing Z of the second row atoms
the 2s-2p energy separation increases and therefore the asymmetric spacing of
the 0" orbitals decreases. This leads to a different ordering of the 30"g and 1nu
orbitals depending on whether the molecule is lighter or heavier than N 2. Also,
of course, the electron occupation of the MOs changes through the second row
series. For example, the Ing orbital is empty for N 2, halffull for O 2 and filled for
F 2' In the following we shall denote empty orbitals with an asterisk label, e.g.,
n;
1 for the N 2 molecule.
Because carbon, nitrogen, and oxygen have similar orbital energies for the
atomic 2s and 2p orbitals, MO theory predicts very similar molecular orbitals
and orbital energies for N2 and isoelectronic CO. This is supported by experi-
ment [3.16, 17J and ab initio theory [3.18J and a comparison of the calculated
orbital energies [3.18J is shown in Fig. 2.5, together with the respective orbital
 3.2 Some Molecular Orbitals and Irreducible Representations 51

contours. The MOs of CO cannot be labeled by g and u since there is no

inversion symmetry in the molecule, i.e., the atomic contributions from carbon
and oxygen to the MOs are different. For example, because oxygen is more
electronegative than carbon the bonding MOs tend to have more oxygen, the
anti bonding MOs more carbon character (Fig. 2.5). The Is orbital of oxygen is
the 10", that of carbon the 20" MO.
So far we have constructed MOs without the explicit use of symmetry
although we have, at one point, made use of it. In considering the mixing of the
2s and 2p atomic orbitals in the diatomics we have only allowed the 2s and 2pz
orbitals to mix, not the 2s and 2px and 2py orbitals. This is a result of symmetry
which is most elegantly handled by group theory. The simplest way to take
symmetry into account in constructing MOs is to use the irreducible representa-
tions and character tables [3.11, 14] for the point group of interest. In the
literature, capital letters are typically used for the irreducible representations of
the point groups and small letters for the labeling of orbitals, and we shall do the
same here. It is convention to take the principal symmetry axis of the molecule
as the z-axis.
Let us consider the simplest case, that of a heteronucIear diatomic, e.g., CO.
The CO molecule has C oov symmetry and from the appropriate character table
listed in Table 3.1 we can find that the L representation transforms like z and
therefore characterizes the symmetry properties of the 2pz orbital. The spher-
ically symmetric 2s atomic orbital is represented by the function x 2 + y2 + Z2,
which also transforms like L. In contrast, according to Table 3.1 the 2px and 2py
atomic orbitals associated with the functions x and y transform like the n
representation. The important point in constructing MOs is that only orbitals of
the same symmetry, i.e., belonging to the same irreducible representation, can mix
[3.8, 10, 11, 14]. For CO the 2pz and 2s atomic orbitals have L symmetry and
can therefore mix while the 2px and 2py orbitals have n symmetry and cannot
mix with either the 2pz or 2s orbitals.
The N2 molecule has Dooh symmetry and with respect to the inversion center
of the molecule we can symmetrically combine two 2pz atomic orbitals on each
N to obtain a symmetry adapted bonding orbital which transforms like Z2 (no
sign change upon inversion) and which according to Table 3.1 corresponds to
Lg • Similarly, two 2s atomic orbitals on each N can be combined such that the
symmetry adapted combination transforms like Z2 and therefore corresponds to
Lg , as well. These two bonding combinations are allowed to mix. The corres-
ponding 2s and 2pz anti bonding combinations each transform like z, i.e., switch
sign upon inversion, and according to Table 3.1 they each belong to the
representation Lu and therefore are allowed to mix. In contrast, the 2px and 2py
orbitals and all symmetry adapted combinations belong to the representations
nu and ng and cannot mix with the 2s orbitals.
Similar arguments to those for N2 can also be applied to the CO 2 molecule
which also has Dooh symmetry. Because the atomic orbitals of three atoms are
involved, a larger number of MOs results, in particular, we obtain two empty
antibonding MOs of 0" symmetry, the 50"; and 40"~ orbitals, and one empty n*,
52 3. Symmetry and Molecular Orbitals

Table 3.1. Selected abbreviated character tables

C oov E 2Ct, 00 (Jv

L Z, X 2 + y2, Z2
II 2 2cos¢ 0 (x, y), (xz, yz)

Dooh E 2Ct, 00 (Jv 2St, 00 C2

L. 1 x2 + y2, Z2

II. 2 2cos¢ 0 2 -2cos¢ 0 (xy, yz)

Lu 1 1 -1 -1 -1 z
IIu 2 2cos¢ 0 -2 2cos¢ 0 (x, y)

C2v E C2 (Jv (J~

At 1 Z, x 2 , y2, Z2
A2 -1 -1 R" xy
Bt -1 1 -1 x, R y, xz
B2 -1 -1 y, R" yz

C 3v E 2C 3 3(Jv

At Z, x 2 + y2, Z2
A2 1 -1 Rz
E 2 -1 0 (x, y), (R" Ry), (x 2 - y2, xy), (xz, yz)

Td E 8C 3 3C 2 6S 4 6(Jd

At 1 1 1 1 1 (x2 + y2 + Z2)
A2 1 1 1 -1 -1
E 2 -\ 2 0 0 (x2 _ y2), (2Z2 _ x2 _ y2)
Tt 3 0 -1 1 -1
T2 3 0 -\ -1 1 (x, y, z), (xy, xz, yZ)

the 2n:, orbital. The highest occupied molecular orbital (HOMO) and lowest
unoccupied (LUMO) molecular orbitals of CO 2 are shown in Fig. 3.2. The Is
orbital of oxygen is the nearly degenerate 1au and lag pair, and the Is orbital of
carbon is the 2ag orbital. Note that the Is orbital of carbon is nondegenerate and
gerade since the carbon atom is located in the inversion center of the molecule.
We shall see that the inversion symmetry has important consequences and leads
to different oxygen and carbon K-shell spectra.
 3.2 Some Molecular Orbitals and Irreducible Representations 53

Frontier Orbitals of CO 2 Fig. 3.2. Plot of the highest occupied

(HOMO) and lowest unoccupied (LUMO)
molecular orbitals for CO 2 • labeled by their
symmetry. taken from [3.8]

5u'g

3.2.2 lJydrogen Fluoride, Water, Ammonia, and Methane

Let us now consider bonds between hydrogen and second row atoms. The
simplest examples are the molecules hydrogen fluoride (HF), water (H 2 0),
ammonia (NH 3 ), and methane (CH 4 ) which are isoelectronic with neon. For all
four molecules MOs are constructed from the 2s and 2p orbitals of the second
row atoms and the hydrogen Is orbitals, under the symmetry constraints
dictated by the point groups of the molecules. From the Is orbitals of the off-
center hydrogens we can form symmetry adapted combinations corresponding
to a particular irreducible representation.
Figure 3.3 shows the MOs of HF, H 2 0, NH 3 , and CH 4 , labeled by their
symmetry, as a function of the orbital energies calculated by Snyder and Basch
[3.18]. We also show schematically the chosen molecular coordinate system and
the atomic orbital composition of the MOs. The figure is intended as a guide for
the following discussion. HF has the same symmetry as CO (Ca)V ) and according
to Table 3.1 the fluorine 2s and 2pz orbitals are allowed to mix and interact with
the hydrogen Is orbital. This gives rise to three a orbitals, a pair of bonding
orbitals, 2a and 3a, and an empty 4a* anti bonding orbital. The 2a orbital has
larger 2s and the 3a orbital more 2pz character. The 4a* orbital contains both 2s
54 3. Symmetry and Molecular Orbitals

HF Coov H2 O C 2v NH3 C 3v CH 4 Td

~' rlL ~ @
-_ ... _-
x

10 ~ 2p z
25
~2bi ~
4a* 1
__1_* =~~ ~2Lr~
4a'
f-
-
212 ~.®

-~~~---
~ @$
5
0 &- - - - - - - - - - ----------

$! ~ 1t2>-~
_ 2py
- 10 ~ ~
>
~ 2px 2py ~~
- 15
...>- 17r -r~
~1* ~)-r ~
. ~
0)

II>
c: -20 ~~ ~
"""~~ 2px 2py """

2.,
'
w
2
~
:0 -25
2PZ
25
Px
25 --
~ '®
0 2PZ @j
-30 f-
"""~ ~"""
~

25
2P Z
-35

- 40
25
2p z
~
~
T ~ f-

~
~

}o:.
-45

-W
15 '
t~
1a _.
-----@ ~ ~ ~ 1
-- ...
Fig. 3.3. Correlation between orbital energies for the isoelectronic molecules hydrogen fluoride
(HF), water (H 2 0), ammonia (NH3)' and methane (CH 4 ) . The orbital energies are taken from the
self-consistent field calculation of Snyder and Basch [3.18] and the MOs are labeled by their
irreducible representation in the indicated point groups of the molecules. Note that for H 2 0 the
irreducible presentations b. and b2 depend on the choice of the x- and y-axes. For each MO the
atomic orbital composition is shown. For HF, H 2 0 , and NH3 we have qualitatively followed the
MO composition calculated by Snyder and Basch, while the MOs for CH 4 are in the coordinate
system shown in the figure, which is also used for the canonical MOs tabulated in Table 3.2

and 2pz character [3.18]. The fluorine 2px and 2py orbitals form a pair of 11:
orbitals which are non bonding since there is no 11: orbital on the hydrogen. The
localized fluorine 1s orbital is given the 10' molecular label.
H 2 0 has C 2v symmetry and we choose the z-axis along the C 2 axis and the y-
axis perpendicular to the molecular plane. From table 3.1 the oxygen 1s and 2s
orbitals and the 2pz orbital can be seen to transform like the A 1, the 2px orbital
 3.3 Molecular Orbitals, Equivalent Orbitals and Hybrid Orbitals 55

like the BI and the 2py orbital like the B2 irreducible representations. The
localized oxygen Is orbital is given the la l label. Mixing of the 2s and 2pz
orbitals with the appropriate symmetry adapted pairs of hydrogen orbitals
results in three bonding, 2a l , Ib l and 3a l , and two antibonding, 4a! and 2b!,
MOs. The oxygen 2py orbital forms a non bonding n, the Ib 2 orbital. Another
way of constructing MOs for a molecule like H 2 0, using simple (1 and n
symmetry considerations with respect to symmetry planes in the molecule, is
discussed by Jorgensen and Salem [3.8] for methylene (CH 2 ).
NH3 has C3v symmetry and we choose the z-axis along the C 3 axis. Because
of the threefold symmetry in the x-y plane, the 2px and 2py orbitals are
degenerate and according to the character table they correspond to the irreduc-
ible representation E. Similar to H 2 0 the 2pz and all s orbitals of nitrogen
correspond to the Al representation, and we denote the nitrogen Is orbital as
la l . Mixing of the 2s and 2pz with appropriate symmetry adapted combinations
of the three hydrogen Is orbitals leads to the bonding 2a l , Ie and 3a l , and
antibonding 4a! and 2e* MOs shown in Fig. 3.3. Inspection of the wave-
functions [3.18] reveals that the 3a l MO has little hydrogen character and is,
essentially, the nitrogen lone pair orbital. Again, the MOs can also be derived
from considerations of (1 and n symmetries with respect to certain molecular
planes as discussed by Jorgensen and Salem [3.8] for the methyl (CH 3) radical.
Thus the 4a! MO in NH3 can be called a N-H (1* and the 2e* a N-H n* orbital.
For CH 4 the symmetry is that of the tetrahedral group Td and the cubic
symmetry requires all 2p orbitals to be degenerate, corresponding to the
representation T2 • Again all carbon s orbitals belong to the symmetric repres-
entation Al with the carbon Is or la l orbital lowest in energy. Note that the
mixing of the 2s and 2pz orbitals is symmetry forbidden. The MOs resulting
from combinations of the carbon 2px, 2py, and 2pz orbitals and symmetry
adapted combinations of the four hydrogen Is orbitals, labeled hI' h2' h3' and
h4' depend on the choice of the coordinate system. The schematic pictures for
the bonding 2al and It2 and anti bonding 3a! and 2t! MOs in Fig. 3.3 refer to
the coordinate system shown [3.10] and differ from those given by Jorgensen
and Salem [3.8]. Note in particular that the 3a! LUMO does not contain any p-
orbital component, which as we shall see is important in conjunction with the
dipole selection rule.

3.3 Molecular Orbitals, Equivalent Orbitals and Hybrid Orbitals

3.3.1 Molecular Orbital Versus Valence Bond Theory

For the description of molecules we have, so far, used MO theory, which is based
on the construction of MOs from the orbitals of the individual atoms, under
consideration of symmetry. The success of this LCAO scheme is based on its
mathematical convenience for the calculation of ionization potentials, which via
Koopmans' theorem can be associated with the orbital energies of the canonical
56 3. Symmetry and Molecular Orbitals

MOs. On the other hand, organic chemists have long used another model, based
on the sharing of pairs of electrons, to explain the similarity and additivity of
important "bond characteristics", such as bond energies and geometries, in
certain classes of molecules [3.19]. This model, originated by Lewis, was
developed by Pauling and others in the 1930s into the quantum mechanical
Valence Bond Theory [3.6]. Here we shall make use of some of the concepts of
the valence-based theories because they are very useful, if not fundamental, for
the classification of molecules and/or discussion of the properties of large
molecules. In particular, we shall consider an important subgroup of molecules,
the hydrocarbons, and develop simple concepts to explain many of their
properties.
Our earlier MO description of methane (CH 4 ) showed well the correspond-
ence between atomic orbitals, MOs and one-electron binding energies. In
particular, because of symmetry, the bonding between carbon and the four
hydrogens resulted in four bonding MOs, three degenerate 1t2 and a single 2a 1
orbital, shown in Fig. 3.3. However, in the MO model there is no indication that,
in fact, all four carbon-hydrogen bonds are chemically equivalent, e.g., have
identical bond lengths (~ 1.1 A), bond energies ( ~ 100 kcaljmol), and stretching
force constants (~500 Nm - 1). This equivalence of the carbon-hydrogen bonds
naturally emerges from the valence-based theorices, either the octet electron rule
in Lewis' theory or the covalent electron-pair bond in Valence Bond Theory. In
both valence-based theories each C-H bond consists of a shared electron pair.
One important concept born out of the electron-pair bond model is that of
hybridization. This mathematical concept consists of constructing equivalent
hybrid orbitals from combinations of atomic orbitals. For carbon the lowest
electronic configuration is (ls)2(2s)2(2Px)(2py) with two unpaired electrons. The
basis of the hybrid orbitals is the excited configuration (ls)2(2s)(2Px)(2py) (2pz)
with four unpaired electrons. Although this configuration lies about 100kcalj
mol or 4.3 eV above the ground state, this energy can be retrieved by the ability
of the excited carbon atom to form more than two bonds. For example, for
methane four hybrids are formed from a linear combination of the four atomic
2px, 2py, 2pz, and 2s functions, and because each hybrid consists of one sand
three p orbitals the hybrid is called an Sp3 hybrid. Similarly, we can form Sp2
hybrids from two p and one s orbital, and an Spl or simply sp hybrid from one p
and one s orbital (the "unused" p orbitals form 1t bonds, see later). Wave-
functions for the three types of hybridization are given in Table 3.2.
Hybridization forms a useful intellectual bridge between a mathematical
technique and simple structural ideas. For example, Sp3 hybrids form tetra-
hedral bonds (bond angle ~ 110°), Sp2 hybrids trigonal bonds (bond angle
~ 120°), and sp hybrids digonal bonds (bond angle 180°). Using the hybrid
concept, large molecules may be assembled by means of "localized" hybrid
bonds and it is possible to calculate many molecular properties such as heats of
formation, geometries, and dipole moments by assuming that the contributions
from the individual "localized" bonds are additive [3.22].
On first inspection, the molecular orbital and hybrid orbital concepts appear
to have little or no connection. However, in a series of papers beginning in 1949
 3.3 Molecular Orbitals, Equivalent Orbitals and Hybrid Orbitals 57

Table 3.2. CH 4 molecular and equivalent orbitals and carbon hybrid orbitals

Canonical CH 4 MOs for the tetrahedral group T., [3.20, 21]8

tP, (Ad = 0.5812s) + 0.19(lh,) + Ih 2) + Ih3) + Ih4 »)
tP 2 (T2 ) = 0.5512px) + 0.32(lh,) -lh 2) + Ih3) - Ih4 »)
tP 3 (T2 ) = 0.5512py) + 0.32(lh, ) + Ih 2) -l h3) - Ih4 »)

tP4 (T2 ) = 0.5512pz) + 0.32(lh,) - Ih 2) - Ih3) + Ih 4 »)

Equivalent CH 4 orbitals [3.20, 21]8

tP', = !(tPdA,) + tP 2 (12) + tP 3 (12) + tP4 (12))

= 0.2912s) + 0.28(12px) + 12p,) + 12pz») + 0.58Ih l ) - 0.07(1h2) + Ih3) + Ih4 »)

tP~ = !(tPdAd - tP 2 (12) + tP 3 (12) - tP4 (12))

= 0.2912s) + 0.28( - 12px) + 12py) - 12pz») + 0.58Ih2) - 0.07(1h,) + Ih3) + Ih4 »)

tP~ = !(tPdA,) + tP2 (12) - tP 3 (12) - tP4 (12))

= 0.2912s) + 0.28(12px) -12py) -12pz») + 0.58Ih3) - 0.07(lh l ) + Ih 2) + Ih4 »)

tP~ = !(tP, (Ad - tP 2 (12) - tP 3 (12) + tP4 (12))
= 0.2912s) + 0.28( - 12px) - 12py) + 12pz») + 0.58Ih 4 ) - 0.07(1 hi ) + Ih 2) + Ih3»)

Sp3 hybrids [3.21]

rPl = H12s) + 12px) + 12py) + 12pz»)

rP2 = !(12s) -12px) + 12py) -12pz»)
rP3 = !(12s) + 12px) - 12py) - 12pz»)
rP4 = !(l2s) -12px) - 12py) + 12pz»)
Sp2 hybrids [3.21]
I
1/1,= J3[12s)+J21 2Pz)]

1/12= ~[12s)+AI2PY)- ~12Pz)]

1/13 =_1 [12S) -
J3
fi 12P ) _J2
"';2 Y
_I 12PZ)]

sp hybrids [3.21]
I
XI = J2 [l2s) + 12pz)]

I
X2= J2[12S)-12Pz )]

8 The 2s orbital is orthogonalized to the Is orbital and the small contribution of the Is orbital in
tP I (A I) has been neglected
58 3. Symmetry and Molecular Orbitals

Lennard-Jones et al. [3.23, 24] showed that equivalent or transferrable bond

properties could be understood using MO theory, the key being the determin-
antal description of many electron wavefunctions. We have already encountered
the basic concept underlying this idea in conjunction with the canonical
Hartree-Fock equations (2.28). These were obtained from the general HF
equations (2.24) by a unitary transformation which diagonalized the Fock
operator. The canonical MOs cP i for methane obtained with a minimal basis
set of Slater orbitals by the Hartree-F ock method are listed in Table 3.2 [3.25],
labeled by their irreducible representations. These orbitals may be transformed
into the set of equivalent orbitals or valence orbitals cP;, also listed in Table 3.2, by
a suitable unitary transformation, i.e., the linear combinations indicated in the
table.
From the atomic composition of the equivalent orbitals it is apparent that
they consist of two contributions, "localized' partly on the carbon atom and
partly on one of the four hydrogen atoms. At this point it is important to realize
that the "localization" of electrons implied by the composition of equivalent-
orbital wavefunctions is no real physical but rather a mathematical phenom-
enon. The connection between equivalent orbitals and hybrid orbitals is estab-
lished by the fact that, except for an overall normalization factor of 2, the carbon
contribution to the equivalent orbitals is nearly identical to the carbon Sp3
hybrid orbitals listed in Table 3.2.

3.3.2 Ionization Potentials in Methane

Since valence or equivalent orbitals are associated with the non-diagonal HF
equation (2.24) they do not directly yield ionization potentials but, according to
(2.24) and (2.28), IPs may be obtained by solving the eigenvalue equations [3.26]
N
L
k=l
AikcPk = EcP i , (3.1)

i.e., the secular determinant

(3.2)

Here the matrix elements Aik correspond to those of the nondiagonal Fock
operator. As discussed by Hall [3.26] for methane the matrix Aik for the four
equivalent valence orbitals is given by

a b b b)
b a b b
(
Aij= b b a b . (3.3)

b b b a

The diagonal matrix elements a are the self-energies of the equivalent

orbitals, i.e., the C-H bonds, and the off-diagonal terms represent the interaction
 3.3 Molecular Orbitals, Equivalent Orbitals and Hybrid Orbitals 59

energies. Because of the tetrahedral symmetry each equivalent orbital can

interact with the other three, and all interactions are the same. The above matrix
can be transformed into the following diagonal form by means of a unitary
transformation:

a + 3b 0 o
( o a-b o oo ).
o 0 a-b o (3.4)
o 0 o a-b
The roots of the diagonal matrix correspond to IPs, similar to the case of the
diagonal HF equations. The single root (a + 3b) represents the binding energy of
the 2a 1 orbital, and the triple roots (a - b) are the binding energies of the triply
degenerate It2 MO.
Using experimental binding energies of 14.4 eV for the It2 and 22.9 eV for the
2a 1 MOs of methane [3.13] we can determine the parameters a = -16.5eV and
b = -2.1 eV. In the equivalent orbital scheme one can therefore view methane
as having four equivalent C-H bonds with a self-energy of 16.5 eV. The fourfold
degeneracy of this valence state is lifted by interaction of the equivalent orbitals
such that the energies of the resulting two states are the lowest two IPs of the
molecule, i.e., those of the MOs derived from the atomic 2p and 2s orbitals of
carbon.

3.3.3 Bonding in Ethane, Ethylene, and Acetylene

The usefulness of hybrid orbitals is elegantly demonstrated by considering the
bonding in the di-carbon molecules ethane (C 2 H 6 ), ethylene (C 2 H 4 ), and
acetylene (C 2 H 2 ) (Fig. 3.4). The main difference in bonding between the three
molecules occurs in their C-C bonds, and one may compose the associated
molecular orbitals in a particularly simple fashion from carbon hybrid orbitals.
Although the number of hydrogen atoms and the C-H bond geometries change,
the C-H bond energies [3.27] and bond lengths [3.28] are very similar in all
three molecules. The C-H bonds in all hydrocarbons lead to characteristic
resonance structures in K-shell excitation spectra which are very similar and
distinct from those due to C-C bonds. Therefore, it is a good approximation for
our purpose to separate the C-H from the C-C bonds and focus our discussion
on the bonding between the two carbon atoms.
For ethane, each of the four carbon Sp3 hybrid orbitals forms a separate
bond, either to another carbon atom or one of the three hydrogen atoms, and
the carbon bonds are said to be "saturated". If we choose the z-axis of our
coordinate system along the C-C bond, we can form C-C bonds by hybridiza-
tion of the atomic 2s and 2pz orbitals on each carbon atom as shown in Fig. 3.4,
while the C-H bonds are formed by mixing of symmetry adapted combinations
of hydrogen Is orbitals with carbon 2s-2pz or 2Px-2py combinations. All bonds
are composed of carbon Sp3 hybrids which can be constructed in our coordinate
60 3. Symmetry and Molecular Orbitals

Single Bond Ethane

u~c (3a 2u )

Double Bond Ethylene

"cc (1b 3g )

"cc
-+t-

Triple Bond Acetylene

"cc (1" g)
"~c

Fig. 3.4. Formation of C- C bonding and antibonding (denoted by an asterisk) orbitals from atomic
hybrid orbitals for ethane (C 2 H 6 ), ethylene (C 2 H4)' and acetylene (C 2 H 2 ). For a C atom four hybrid
orbitals can be formed by superposition of atomic 2s and 2px, 2py, and 2p, wavefunctions. For
ethane three hybrids on each C atom are used for bonding to hydrogen atoms while the fourth forms
the C- C bond. If we choose the C-C internuclear axis as the z-axis, a C-C (J bond is formed from
hybids of 2s and 2p, atomic character, as indicated. Two (J orbitals result, a bonding orbital (Jcc with
in-phase and an antibonding orbital (J~c with out-of-phase orbital amplitudes on adjacent atoms,
respectively. The C-C bond in ethane is said to be a single, saturated bond of Sp3 character. For
ethylene, the C-C (J bond is stabilized and shortened by an additionaln bond, originating from 2px
atomic orbitals. As for the (J bond, bonding nee and anti bonding n~e orbitals exist. Ethylene is
therefore double bonded and the C=C bond has Sp 2 character. Acetylene has a second n bond
originating from the atomic 2py orbital. The bonding and anti bonding n states are energetically
degenerate, respectively. The resulting C",C bond is called a sp hybridized triple bond. The shapes
of all orbitals on the left side are just schematic and indicate the position of nodes and the signs of the
wavefunctions. Calculated wavefunctions of the anti bonding orbitals including their group theoret-
icallabels, taken from [3.8], are shown on the right side. For the (J~e orbitals we have selected the
ones with the most C-C character from the various orbitals [3.8]
 3.4 Interactions Between Localized Orbitals: Conjugation 61

system by a linear combination of the Sp3 hybrids listed in Table 3.2. The angle
between any two bonds is ~ 110°. The symmetry adapted combinations of the
atomic 2s and 2p. orbitals lead to two C-C bond orbitals consisting of a filled
bonding ace orbital and an empty antibonding a~c orbital as illustrated in
Fig. 3.4. A three-dimensional picture of the anti bonding a~c 3a 2u orbital for
ethane, taken from [3.8], is also shown.
In the planar molecule ethylene we can explain all in-plane bonding by use of
Sp2 hybrids. Again we choose the z-axis of our coordinate system along the C-C
bond and use a coordinate-adjusted combination of the three Sp2 hybrids, listed
in Table 3.2, to account for the three in-plane C-H and C-C bonds. Note that
the bonds are at angles of ~ 120° with respect to one another. The carbon 2px
atomic orbitals, which are perpendicular to the molecular plane have not yet
been used and we can make a C-C n bond out of them. The so-formed n system,
composed of a bonding and an anti bonding MO, shown in Fig. 3.4, is ortho-
gonal to the in-plane a C-C bonds. This orthogonality is the foundation for the
separate treatment of the a and n bonds in hydrocarbons, underlying Ruckel
theory [3.10]. Illustrations of the antibonding n~c 1b 3g and a~c 4au orbitals for
ethylene [3.8] shown in Fig. 3.4 reveal their symmetry.
Finally, triple bonded acetylene has two orthogonal, energetically degener-
ate n orbitals which are orthogonal to the C-H and C-C a system composed of

n:
carbon 2s and 2p. atomic orbitals, i.e., the sp hybrids listed in Table 3.2. The two
anti bonding 1 orbitals, together with the 4a~ antibonding orbitals [3.8] are
plotted in the bottom right corner of Fig. 3.4.

3.4 Interactions Between Localized Orbitals: Conjugation

To facilitate the understanding of the bonding in the simple pseudo-diatomic

hydrocarbons (the prefix "pseudo" refers to the neglect of the C-H bonds), we
have in the last section introduced the "equivalent orbital" and "hybrid orbital"
concepts. For even larger molecules, e.g., hydrocarbon chains or rings, we can go
one step further. We use equivalent or hybrid orbitals to describe "localized"
orbitals or bonds and treat interactions between such orbitals or bonds as a
perturbation. Thus we account for delocalization or conjugation effects in a
perturbative fashion [3.22]. This view is supported by the fact that, in general,
we can write any MO t/li as a linear combination of equivalent or hybrid orbitals
according to

(3.5)

since "localized" bond orbitals C/Jk are themselves constructed from atomic
orbitals. Thus in our approach we form MOs t/li by a perturbative coupling of
individual C/Jk's. We now introduce a Hamiltonian .Yf such that the diagonal
62 3. Symmetry and Molecular Orbitals

matrix elements

(3.6)

correspond to characteristic "energies", the self-energies, of the "localized"

orbitals tPk • This is the same concept used for methane in the previous section.
The off-diagonal matrix elements

(3.7)

represent the orbital-orbital interaction energies. Furthermore, we assume that

the orbitals tP j are orthonormal,

(3.8)

The zero overlap assumption expressed by (3.8) simplifies the corresponding

secular equations for the energies, similar to the conventional Hiickel treatment
[3.10].

3.4.1 First and Second Order Perturbation Treatment

Let us consider the simple case of two interacting orbitals, represented by the
interaction matrix

( Al B12), (3.9)
B21 A2

whereB12 = B21 = B. If the two orbitals are energetically degenerate, Al = A2

= A, we have the well known case of first order perturbation and we obtain two
split levels with energies

El =A - B, (3.10)

and

E2 = A + B, (3.11)

as shown in Fig. 3.5. Here we have defined the interaction energy B as a negative
quantity. For the corresponding wavefunctions we obtain

(3.12)

and

(3.13)
 3.4 Interactions Between Localized Orbitals: Conjugation 63

First Order Interaction Fig. 3.5. Schematic energy level

diagram for the interaction of two
<1>,-<1>2 orbitals. The strong first order in-
A- S ... .. ....... .... . . .
/ 1'J:K)9C)\ teraction between energetically
degenerate orbitals q" and q,2 with
A ..... .-!!...../ \~ ...... A energy A leads to a higher energy
I'J:K) \ / ~ antibonding orbital q" - q,2 and
\ /
A + 8 .• . . . .• . . .... . . . . .\ <1> , +<1>2 I
a lower energy bonding orbital
q" + q,2. which are separated by
~ an energy 12BI, where the interac-
Second Order Interaction tion energy B is negative. The
weaker second order interaction
8 between energetically nondegener-
'1" +-- '~2
A,-A2 S2 ate orbitals with energies A, and A2
<1>, / i ............. A, + A -A
A, .... .. _ _ _ / ®oC>@) , 2 results in a repulsion between the
®oC> \ \ energy levels. The energies and
\ \
\ \ wavefunctions of the perturbed sys-
\ \ tem are given in the lower diagram
\ \
\ \ ~'2
82 \ ~ / - - _ •.•. • . A2
A 2 - - - · ·· · ···· · ·
A, - A2 B
/ 0
<I'2 - --<r"
A, - A2

If the two interacting states are nondegenerate, say Al > A 2 , and their separa-
tion is large compared to the perturbation, IBI ~ Al - A 2 , we have the other
familiar case of second order perturbation. In this case the interaction pushes the
two states apart according to
B2
EI = Al + Al - A2 (3.14)

and

(3.15)

as shown in Fig. 3.5 with wavefunctions

(3.16)

and

(3.17)

Here c is a normalization constant. It can be seen from (3.16) and (3.17) that the
wavefunctions of the composite system are predominantly those of the two
64 3. Symmetry and Molecular Orbitals

respective "localized" components since IBI ~ A1 - A 2 . Note, however, that the

change in the energies given by (3.14) and (3.15) may still be sizeable since the
perturbative correction is quadratic in B.

3.4.2 Interactions in Chain-Like Hydrocarbons

In order to apply the above concept, let us consider the example of interacting
"localized" p-orbitals in the polyenes and polyines, i.e., hydrocarbon chains with
alternating C-C double and single and triple and single bonds, respectively. For
the polyene series the starting point is ethylene (H 2 C=CH 2 ), characterized by
"localized" p-orbitals on each C atom, which interact to form a 1t bond. The next
larger molecule is butadiene (H 2 C=CH-CH=CH 2 ) with four interacting p-
orbitals. Note that in allene (H 2 C = C = CH 2 ), with two adjacent double bonds,
the adjacent 1t systems are orthogonal, resulting from interaction of two pairs of
orthogonal p-orbitals, and therefore the 1t system is not delocalized. The third
member of the polyene series with six interacting p-orbitals is hexatriene
(H 2 C = CH-CH = CH-CH = CH 2 ). If we replace the double bonds in the above
molecules by triple bonds we obtain the polyines acetylene (HC == CH), di-
acetylene (HC == C-C == CH), triacetylene HC == C-C == C-C == CH), etc., which
can be treated similarly to the polyenes with two orthogonal p-orbitals on each
C atom.
The general treatment of the polyenes and polyines requires consideration of
the interaction between the various atomic p-orbitals. This is done in Huckel
theory by starting from identical p-orbitals on the individual C atoms, charac-
terized by a self-energy IX, and considering nearest neighbor interactions {3
between the atomic p-orbitals [3.10]. For ethylene this yields the orbital
interaction matrix

(3.18)

and the eigenvalues are 81,2 = IX ± {3 such that the resulting filled bonding and
empty anti bonding 1t orbitals are separated by 2{3. Considering only nearest
neighbor interactions between p-orbitals, the matrix for butadiene is

IX {3 0 0)
{3 IX {3 0
( (3.19)
O{3IX{3 ,
o 0 {3 IX
and the bonding orbitals are at energies 8 1 = IX + 1.62{3 and 8 2 = IX + O.62{3
(note that {3 is negative in the conventional Huckel treatment) and the anti-
bonding orbitals are at 8 3 = IX - O.62{3 and 8 4 = IX - 1.62{3. Figure 3.6 illustrates
the interaction and resulting MOs and energy levels for the cases of ethylene and
butadiene, discussed above.
 3.4 Interactions Between Localized Orbitals: Conjugation 65

C atom Ethylene Butadiene

Fig. 3.6. Interaction of atomic p-orbitals on carbon atoms to form the 1t systems of ethylene
(H 2 C=CH 2 ) and butadiene (H 2 C=CH-CH=CH 2 ). For ethylene the interaction results in an
antibonding 1t: and bonding 1t. orbital. For butadiene (H 2 C=CH-CH=CH 2 ) there is an inter-
action between two (identical) 1t systems, 1t. and 1tb' and a splitting within the antibonding and
bonding system occurs, as shown. In first order perturbation theory the splitting within the
antibonding and bonding systems is treated independently. In second order, the interaction between
the two manifolds leads to an increased overall splitting but does not effect the internal splitting
within the bonding and anti bonding manifolds

From the examples it is apparent how the Hiickel scheme can be used to
predict the energies of the bonding and antibonding orbitals of a polyene or
polyine chain of any length. In fact, it is possible to obtain a general expression
for the Hiickel energies for the interaction of n orbitals in a chain of n atoms
[3.10]

em = IX + 2{3COS(~).
n+l
(3.20)

The eigenvalues are labeled by the index m = 1, 2, ... , n. For a polyene or

polyine n is an even number, and it is twice the number of double bonds. From
(3.20) we see that in the limit of a long chain, n -+ 00, the energies become a
continuous band with peaks at the extreme values IX + 2{3 and IX - 2{3. The
splitting in the anti-bonding and bonding manifolds for the polyenes, measured
by means of electron transmission spectroscopy and photoemission, respectively
[3.29], is shown in Fig. 3.7.
Although Hiickel theory is typically used for the description of 1t electron
systems, one of the most beautiful examples of the level splitting predicted by the
theory is that of a (J system, i.e., of the carbon 2s level in the paraffins [3.13,
30--32] shown in Fig. 3.8. In going from methane (CH 4 ) to ethane (H 3 C-CH 3 )
the 2a 1 , or carbon 2s derived orbital, splits into a bonding and anti bonding pair
due to interaction between the two carbon orbitals. For the larger paraffins the
splitting pattern follows that predicted by (3.20), e.g., a triplet for propane
66 3. Symmetry and Molecular Orbitals

Binding Energy reI. to Vacuum Level (eV)

30 20 10 30 25 20

IJi~
(c)
Theory
2. 2. Band

Splitting of1r System in Polyenes 2p l CH 4

~ I I C2 HS

M;
:;
~
~ -4 -4 f I C3 H S

~ C2 HS
i I II n-C4 H lO

&.
~
:{
.~

I, ,
-2 "~ f I I ,'J n-C s H 12
guc: -2
~
~ :e I, n-C s H 14

lYG,'"
W ~

'" 0 o ~
"
c:
.. ii'
I ,j n-C 7H 1S
.!l
ill, I ,i
I,,,
:; -= n-C s H 1S

II
~ +8 +8

~c: I n-C g H 20
., n;20
~+10 +10

.,
c:
.o
:!l
'g +12 +12

"
, Binding Energy reI. to Fermi Level (eV)

Fig.3.7. Splitting of the n system in the polyenes: ethylene, butadiene, cis- and trans-hexatriene, and
all-trans-l,3,5,7-octatetraene [3.29]. The electron affinities of the unoccupied n* leyels were meas-
ured by electron transmission spectroscopy and the ionization potentials of the occupied n system
by photoemission

Fig. 3.8. (a) Splitting of the carbon 2s atomic level in the gas-phase paraffins methane (CH 4 )
through nonane (C 9 Hzo) observed in X-ray photoemission spectroscopy (XPS) [3.13]. Note that at
XPS energies the cross section of the 2s level is enhanced relative to the 2p level. The binding energy
is referenced to the vacuum level. (b) XPS spectrum of the valence band of polyethylene showing the
splitting of the 2s level into two peaks [3.33]. Here the binding energy is referred to the Fermi level
and differs from that in (a) by a work function and extramolecular relaxation shift. (c) Splitting of
the 2s level with increasing paraffin size as calculated by an ab initio molecular orbital calculation
[3.13]. (d) Results of an ab initio calcula-tion of the valence band density of states for polyethylene
where the binding energy scale has been corrected as discussed by Andre et al. [3.34]. In order to
correlate the splitting ofthe 2s band in the paraffins with that in polyethylene (limit of infinitely long
chain) we have aligned the two peaks in the polyethylene density of states with the limits of the 2s
splitting in (c)

(H 3 C-CH 2-CH 3 ), a quartet for butane (H 3 C-CH 2 -CH 2 -CH 3 ), etc. In the long-
chain limit, i.e., for polyethylene ([-CH 2-CH 2 - ]n), two peaks separated by
about twice the splitting for ethane are found [3.30] as predicted by (3.20). Note,
though, that the splitting of the mainly 2p derived It 2 level of methane through
the paraffin series is more complicated than that ofthe 2s derived 2a 1 level, both
because of mixing with hydrogen orbitals, and because some of the anti bonding
 3.5 Splitting of Antibonding Orbitals Due to Bond-Bond Interactions 67

orbitals are unoccupied. In fact, it is transitions to these unoccupied anti bonding

orbitals which give rise to K-shell excitation resonances.

3.5 Splitting of Antibonding Orbitals

Due to Bond-Bond Interactions

3.5.1 The Linear Combination of Bond Orbitals Method

Often, either the bonding or the antibonding orbitals, but not both, are observed
by a given spectroscopic technique. As illustrated in Fig. 3.7, photoemission
[3.35] probes filled bonding orbitals and inverse photoemission [3.36] or
electron transmission spectroscopy [3.29, 37] probes empty antibonding or-
bitals. X-ray absorption spectroscopy also probes unfilled antibonding orbitals
which are the final states of the K-shell transitions. We can therefore simplify
our treatment by considering only the splitting of the anti bonding n* and (1*
orbitals. Hence, rather than starting with atoms we begin with an atomic pair,
i.e., a bond, and consider the energy splitting of the anti bonding orbitals of a pair
caused by first order bond-bond interactions between the pair of atoms, the so-
called Linear Combination of Bond Orbitals (LeBO) model. We neglect second
order interactions between the bonding and anti-bonding manifolds, which are
included in the Huckel treatment given in Sect. 3.4.2. As illustrated by Fig. 3.6,
second order interactions mainly lead to a repulsion between the two manifolds,
not significantly perturbing the internal level splitting within the bonding or
antibonding groups. Note that second order perturbations are, however, im-
portant in the consideration of collective molecular properties, like the total
energy, as discussed by Dewar and Dougherty [3.22].
The LeBO scheme is particularly useful if there is a characteristic "energy"
associated with a bond. We shall see below that this is, in fact, the case in K-shell
excitation spectra, where different molecular bonds are characterized by differ-
ent resonances which occur at specific resonance energies. Interactions between
adjacent bonds can then be treated by first or second order perturbation (Sect.
3.4.1) and lead to a splitting of K-shell resonances or resonance shifts as
schematically shown in Fig. 3.5. The LeBO formulation reduces the dimen-
sionality of the bond matrices by a factor of 2, as illustrated below for the case of
n*-n* interactions in the polyenes and (1*-(1* interactions in the paraffins.

3.5.2 Application to (1 and 1r Bonds in Hydrocarbons

If we define the self-energy of the n* anti bonding orbital of ethylene as A we can
account for the n* splitting in butadiene by an interaction energy B between the
two n bonds (Fig. 3.9). Hence the bond matrix for butadiene is

(3.21)
68 3. Symmetry and Molecular Orbitals

Butadiene Fig. 3.9. Illustration of bond- bond interactions

(conjugation) for the 1[ system in the polyenes and
the (J system in the paraffins, using the correspon-

~:::~~-!(:t ding cases, butadiene and propane, as examples.

For the polyenes the interaction B n - n is between
H--- C ~
. I.. C --- H 1[ bonds belonging to pairs of double bonded

II········· · ~ · · · · ··~\
atoms. For the paraffins the interaction b._. is
between the single bonds of a C-C pair. Overall,
Brr- rr there are always the same number of 1[ and spJ
hybrid orbitals on corresponding members of the
series, e.g., four 1[ orbitals in butadiene and four
spJ hybrid orbitals in propane, six 1[ orbitals in
Propane hexatriene and six spJ hybrid orbitals in butane,
etc.

and the eigenvalues are 81,2 = A ± B. Similarly for hexatriene the bond matrix
and eigenvalues are

U~ n·
and 8 1 = A + fiB , 8 2 = A, and 8 3 = A - fi B. Again, the extension to a
(3.22)

larger chain is obvious and the eigenvalues follow from (3.20). Another inter-
esting example is benzene. In this case the bond matrix is related to that of
hexatriene with an additional off-diagonal matrix element due to the ring
closure, i.e.,

(3.23)

The eigenvalues are 8 1 = A + 2B, and 8 2 , 3 = A - B, such that there are two 11:*
antibonding orbitals, one of which is a degenerate pair. An extension of the
above concepts leads to a general analytic expression for the energy levels of the
11: system in unsaturated cyclic molecules and to Hiickel's rule on aromatic
reactivity [3.10].
As a second example for the LCBO model, let us consider the C-C cr bonds
of a paraffin chain. The starting point of our treatment is the "self-energy"
associated with the C-C anti bonding cr* orbital in ethane (H 3 C-CH 3 ), which is
 3.6 Orbital Orientation, Symmetry, and the Dipole Selection Rule 69

split by an increasing number of bond-bond interactions as we increase the

chain length to propane (H 3C-CH r -CH 3) with two interacting C-C single
bonds, butane (H 3C-CH 2 -CH 2 -CH 3) with three interacting C-C single bonds,
etc. For propane the bond matrix is given by

(3.24)

and the eigenvalues are 61,2 = a ± b. If we only consider nearest neighbor bond
interactions we obtain the following bond matrix for butane:

a
( b
b
a
0)
b , (3.25)
o b a

with eigenvalues 61 = a + fib, 6 2 = a, and 6 3 = a - fib. Comparison be-

tween the 11: interactions in the polyenes and the (T interactions in the paraffins
shows a one-to-one correspondence of the bond matrices and eigenvalues of
propane and butadiene, butane and hexatriene, etc. This has previously been
discussed by Dewar [3.38] in terms of a comparison of 11: conjugation in the
polyenes and (T conjugation in the paraffins. While in the polyenes the
bond-bond interaction B is between 11: systems belonging to pairs of double
bonded atoms, the bond-bond interaction b in the paraffins is between C-C
single bonds, as shown clearly in Fig. 3.9.
This figure also shows that, although there are only three carbon atoms in
propane, there are four carbon hybrid orbitals involved in the C-C bonding,
similar to the four 11: orbitals in butadiene. As pointed out by Dewar [3.38] the
above scheme leads to an equivalent description of the 11: system in benzene and
the (T system in cyclopropane (C3H6)' In cyclopropane there are interactions
between two Sp3 hybrids on each of the carbon atoms and the bond matrix is
given by

a
( b
b b)
a b , (3.26)
b b a

which is identical in structure to that of the 11: system in benzene (3.23).

3.6 Orbital Orientation, Symmetry, and the Dipole Selection Rule

3.6.1 Orbital Orientation and Angular Dependence of the Dipole Matrix Element
One important feature of molecular orbitals is that they have strong directional
character and there is a one-to-one correlation between the spatial orientation
of the orbitals and the molecular geometry. Thus for oriented molecules and
70 3. Symmetry and Molecular Orbitals

polarized X-rays the intensities of resonances associated with, for example, a*

and n* final states should exhibit a dramatic and different angular dependence.
The polarization dependence of the intensity of a particular resonance
associated with a specific molecular orbital can be derived quite generally from
the expression for the X-ray absorption cross section given by (2.8). The angular
dependence is contained in the dipole matrix element and according to (2.8, 11)
we can write for the transition intensity Ii!'

(3.27)

assuming the X-rays are linearly polarized in the direction of the unit vector e.
Let us first evaluate the dipole matrix element <flrl i) in (3.27). We shall restrict
ourselves to K-shell excitation, firstly because of its importance for low-Z atoms
and secondly because it exhibits the strongest polarization-dependent effects.
The initial Is state Ii) = R1s(r) is spherically symmetric and it is to a very
good approximation represented by the atomic Is wavefunction of the excited
atom in the molecule. In a one-electron model, the upper state of a bound-state
transition can be represented by a LCAO wavefunction (2.34) of the correspond-
ing molecular orbital. Because of the localization of the Is initial state, the
atomic valence components of the excited atom in the LCAO wavefunction
dominate in the evaluation of the dipole matrix element. For the second row
atoms, one may therefore consider only these terms and write the final state
wavefunction as a linear combination of atomic 2s and 2p states on the excited
atom, i.e.,

= aR2s(r) + R 2p (r)( b sin fJ cos ¢ + c sin fJ sin ¢ + d cos fJ) , (3.28)

where the coefficients a, b, c, and d give the weight of the atomic orbitals in the
LCAO expansion, and R2s(r) and R 2p (r) are the radial atomic wavefunctions.
Equation (3.28) shows that the maximum amplitude of the final state orbital is in
the direction 0 determined by the superposition of the three p orbitals, namely,
0= bex + cey + dez , where the unit vectors ei are along the axes of our
coordinate system.
We express the position vector in spherical coordinates, r = r(sin fJ cos ¢ ex
e
+ sin fJ sin ¢ ey + cos ez ), the vector matrix element in (3.27) can be evaluated
by integration and we obtain

(3.29)

where

(3.30)

IS the radial dipole matrix element. Thus, according to (3.29), for K-shell
 3.6 Orbital Orientation, Symmetry, and the Dipole Selection Rule 71

excitation, the vector matrix element points in the same direction as the p-
component in the final state orbital on the excited atom and thus the polarization
dependence of the total matrix element can be expressed as a function of the
angle lJ between the direction e of the electric field vector and the direction 0 of
largest amplitude of the final state orbital, namely

(3.31)

As an example, let us consider the 0"* and n* orbitals of a triple bonded

diatomic, e.g., N2 or CO. We orient our coordinate system so that the 0"* orbital,
and therefore the internuclear axis, lies along the z-axis, and the two n* orbitals
lie along the x- and y-axes, and specify the orientation of the unit electric field
vector e by spherical angles (J' and 4J'. The polarization dependence of the
resonance intensity associated with the 0"* molecular orbital final state is then
simply given by

(3.32)

Therefore the 0"* resonance intensity is greatest for E along the internuclear
axis and vanishes when E is perpendicular to it. The polarization dependence of
a resonance associated with the two energetically degenerate n* orbitals can be
derived from (3.31) by integration over all E vector orientations in the x-y plane
and is obtained as the sum of the individual intensities of n* orbitals along ex
and along ey,

Ii/(n) oc le·ex l2+ le·eyl2

oc sin 2 (J' cos 2 4J' + sin 2 (J' sin 2 4J' oc sin 2 (J' • (3.33)

Resonances associated with 0"* and n* orbital final states, therefore, have a
strong and opposite polarization dependence. Equations (3.32) and (3.33) are the
foundation for the determination of molecular orientations on surfaces by
means of NEXAFS and detailed angular effects will be discussed in Chap. 9.
We have so far assumed that the final state has a p orbital component. For a
Is initial state this is the prerequisite for an allowed transition, dictated by the
dipole selection rule. Because the K-shell excitation occurs on a particular atom
due to spatial localization of the Is initial state, it is the local symmetry of the
MO final state on the excited atom which determines whether the transition is
allowed. The importance of spatial localization in K-shell excitation is revealed
by the radial part of the dipole matrix element given by (3.30). Clearly it is the
overlap of the Is and 2p functions near the atomic core which determines the
matrix element. This is the origin of the often used one-center approximation in
the calculation of K-shell X-ray emission spectra [3.39,40]. One simple method
of checking whether a transition from the K -shell to a particular final state is
allowed is to inspect a plot of the MO final state and look for a node, indicating
local p-character. Note that for second row atoms, d and f orbital final states
which also have nodes do not contribute to the MOs. Inspection of Fig. 3.2
72 3. Symmetry and Molecular Orbitals

reveals that in CO 2 transitions from the carbon K-shell are allowed to the 40":
(node) but not to the 50": (no node) MO, while both transitions are allowed for
excitation of the oxygen K-shell.

3.6.2 Group Theory and the Dipole Selection Rule

In many cases plots of the empty MOs are not available and another, more
general, method must be used to determine whether specific transitions are
allowed. Again, group theory is employed. Since the irreducible representations
contain all the symmetry information for a given point group, we can determine
whether the transition matrix element <flrli) is zero or not simply by inspec-
tion of the representations for the initial core state and the MO final state. The
group theoretical method is not only elegant but also of general validity and can
thus be applied to determine the selection rules for transitions between any two
states.
Before we consider this approach, we must discuss different ways of consid-
ering the effect of the core hole. The simplest approach is to use the broken
symmetry of the final state. The broken symmetry is obtained from the ground
state symmetry by assuming that the excited atom is changed by its core hole
and as such is different from other atoms in the molecule with the same atomic
number. In this case the Is initial state transforms like the totally symmetric
representation of the broken-symmetry point group and the selection rules for
the allowed transitions are worked out in the broken symmetry. The second
method treats the core hole as if it were delocalized (which of course in practice it
is not) and in this case the Is initial state corresponds to those irreducible
representations which describe the possible delocalized hole combinations in the
full symmetry of the molecular ground state, and the selection rules are worked
out in this symmetry. The third, and rigorously correct approach, is to consider
the whole set of broken symmetry configurations and form linear combinations
thereof such that the transition can take place within the higher symmetry of the
molecular ground state [3.41, 42].
In practice, the three procedures normally arrive at the same result. For a
quick check of the allowed transitions, it is often convenient to use the second
method since MO calculations are typically carried out in the ground state
molecular symmetry and the MOs published in the literature are labeled with
the irreducible representations of that symmetry.
For a given symmetry and initial and final state representations, the selection
rules are worked out as follows [3.14]. Since the dipole operator r is a vector
with components (x, y, z), the dipole transition will be allowed if the direct product
of the irreducible representations of the initial and final states is or contains the
irreducible representation to which x, y, or z belongs. Furthermore, if we find that
the direct product transforms like x, y, or z, we know from (3.31) that the
transition will be observed strongest if the electric field vector E is pointing in
that direction. The direct product is easily calculated from the respective
character table. First, we calculate the characters of the direct product which are
 3.6 Orbital Orientation, Symmetry, and the Dipole Selection Rule 73

equal to the product of the respective pairs of characters of the representations.

The direct product is then the sum of those irreducible representations whose
characters sum to the calculated characters of the direct product [3.14]. Tables
of direct products are given by Herzberg [3.43].

3.6.3 Applications of Group Theoretical Selection Rules

By way of illustration we will now discuss the expected K-shell spectra for NH3
and CH 4 . In both cases, the symmetry of the molecules in the ground state is
identical to that of the excited state with a hole on the N or C atom, respectively.
Thus we simply consider the selection rules for the molecules in the ground state.
For NH3 the nitrogen Is state transforms like AI' and the empty MOs
transform like Al and E, respectively. According to Table 3.1, for the C 3v point
group the direct product Al x Al = Al transforms like z. Hence the la l -+ 4a I
transition (Fig. 3.3) is allowed and it is strongest for E parallel to z, the symmetry
axis of the NH3 molecule. The second transition from the la l to the 2e orbital is
also allowed since Al x E = E, which transforms like (x, y). This transition is
maximized for E in the x-y plane, perpendicular to the symmetry axis of the
molecule. For CH 4 the la l -+ 3a I transition is forbidden since for the Td point
group the direct product Al x Al = Al transforms like X Z + yZ + zZ. The reason
is, of course, that the 3a I orbital has no p-character, as mentioned earlier. The
transition la l -+ 2t z is allowed since Al x 12 = 12 transforms like (x, y, z). There-
fore, the intensity of this transition has no angular dependence, as would be
expected for cubic symmetry.
COz in its ground state has the symmetry Dooh with the corresponding
character table given in Table 3.1. Let us first consider selection rules for this
symmetry. The allowed transitions follow from a general rule, which forbids
transitions between two states of the same inversion symmetry. Hence g -+ g and
u -+ u transitions are forbidden. The reason is that the dipole operator is un-
gerade with respect to inversion and hence the direct product of initial and final
states must be ungerade, too. For the oxygen K-shell in COz, the initial state is a
nearly degenerate lUg and luu pair and the transitions lUg -+ 2n:, luu -+ 5u:,
and lUg -+ 4u: are allowed (Fig. 3.2). In contrast, for the carbon K-shell excita-
tion, the initial2ug MO is of gerade symmetry only, and therefore the 2ug -+ 5u:
transition is forbidden.
Consideration of the core hole does not change the symmetry for the carbon
K -shell excitation, and therefore the above arguments also apply for this case.
For the oxygen K-shell excitation, however, the effective symmetry created by
the localized hole on one of the oxygen atoms is reduced to C oov . We now need
to work out how the irreducible representations in Doob map into those of C oov .
This is easily done by comparison of the characters for the symmetry operations
which are common to both symmetries. If the characters correlate, the two
respective representations map into each other. Simpler yet, correlation tables
between the irreducible representations of different point groups can be found in
Ibach and Mill's [3.44] and Herzberg's [3.43] books. Comparison of the
74 3. Symmetry and Molecular Orbitals

character tables in Table 3.1 readily shows that I'g and I'u in D oo h symmetry both
correspond to I' in C oo v symmetry, and the same applies for the n representa-
tions. Thus for the effective core-hole-induced C oo v symmetry we have two
empty (1* MOs which can both be reached from the 0 Is state, which is also of (1
symmetry. We therefore obtain the same result, independent of core hole
localization, for both the carbon and oxygen K-edge excitations.
Finally, we shall consider the selection rules for a bent triatomic molecule of
the general form XYX, such as N0 2 • This case will be of importance in later
chapters for the chemisorbed CO 2 and HCOO- species. The evolution of MOs
from a linear triatomic with symmetry Doo h (e.g., CO 2 ) to a bent triatomic
molecule with symmetry C 2v , can be conveniently treated in the form of a Walsh
diagram [3.8, 43] (Fig. 3.10). For the bent molecule we have chosen the z-axis
along the C 2 axis and the x-axis in the molecular plane. We find the upper three
states to be of b l , ai' and b2 symmetry and therefore need to work out the

Walsh Diagram for YX 2

A 5b,
___ l~Y
~x

A 7a,

m
---~50g 0<>G<:>0

A 2b 2I----------:::;:::=----i 21Tu 000

X 4b,
la 2

*X
6a, 11T9 He--o
5a,
l b2 11Tu m~
3b,
30u f><O>OO

A 4a,
40g CKO:>o

X 2b,
3a,
20u
30g
0--0
~

90· 180·
~XYX

Fig.3.10. Walsh diagram for the evolution of molecular orbitals from a linear triatomic molecule of
general form X YX, e.g., CO 2 , to those of a bent triatomic molecule, e.g., N0 2 , as a function of the
bending angle. The MOs are labeled by their irreducible representations. For the bent molecule we
have chosen the z-axis along the twofold symmetry axis and the x-axis in the molecular plane, as
shown by the inset. Note that our choice of the x- and y-axes determines which MOs correspond to
the bl and b2 representations. The labeling would be reversed if the y-axis were chosen in the
molecular plane
 3.7 Spin-Dependent Excitations 75

Table 3.3. Symmetry and polarization of resonances in a bent triatomic molecule X YX'

Core state Transition Polarization

(E vector orientation)

X Is la l -+ 6a l (uT) z
la l -+ 2b 2 (It*) Y
la l -+ 7a l (un z
la l -+ 5b l (un x

X Is Ib l -+ 6al (uT) x
Ib l -+ 2b 2 (It*) Forbidden
Ib l -+ 7a l {un x
Ib l -+ 5b l {un z

Y Is 2a l -+ 6a l {un z
2a l -+ 2b 2 (It*) Y
2a l -+ 7a l {un z
2a l -+ 5b l {un x

• C2v symmetry; the z-axis is in the C2 axis and the x-axis in the molecular plane, and assuming that
the Is ionization potential of atom X is larger than for atom Y

polarization of the transitions from the X 1s and Y 1s levels to these MOs. Let us
first consider the transitions in the full ground state symmetry. The 1s orbital of
the central atom Y (i.e., the 20" MO if we assume that the 1s binding energy of
atom X is larger than of atom Y) clearly transforms as the symmetric repres-
entation Al in the character table (Table 3.1). The 10" MO of the outer atoms X
can be constructed from a symmetric or antisymmetric linear combination of the
two 1s wavefunctions. The symmetric combination transforms like A l , the
antisymmetric combination like B l • Using Table 3.1 we can now work out the
polarization of the various transitions; the results are given in Table 3.3 [3.45].
In the Table we have also listed the selection rules for transitions to the 6al MO,
which is the LUMO for many triatomics, e.g., N0 2 with a O-N-O bond angle
of 134.0°.
For the localized-core-hole case, excitation of the central atom does not
reduce the symmetry, while excitation of the outer atom X results in a symmetry
reduction to C•. The Al and Bl representations in C2v symmetry correspond to
the A' representation in C. and the B2 representation to the A" representation
[3.43]. The X 10" MO transforms like A', and A' - A' transitions are allowed for
E in the molecular x-z plane (0"*), and A' - A" transitions are allowed for
Ell y (n*). Hence we obtain the same polarization dependence as for the full
ground state symmetry.

3.7 Spin-Dependent Excitations

Thus far we have tacitly assumed that it does not matter whether we excite the
spin-down or the spin-up electron in the K-shell. This is in fact true for alI closed
76 3. Symmetry and Molecular Orbitals

shell atomic and molecular systems. The reason is that for electric dipole
excitations there is no difference in exchange interaction in closed shell systems
between the different possible final states attainable by K-shell excitation. In
short, the dipole selection rule states that the total spin is conserved during
excitation because the dipole operator does not act on spin. For ionization, the
photoelectron therefore always has opposite spin to that of the electron left
behind in the K-shell and the two possible final states are energetically degener-
ate, and therefore there is only one IP. For bound state excitations the situation
is similar, with the electron in the K-shell and the excited electron in a Rydberg
or molecular orbital having opposite spins. Again, the two possible spin config-
urations for a given two-level system are energetically equivalent and there is
one transition energy.
Let us discuss three examples to illustrate spin-dependent excitations,
namely the K-shell spectra of the molecules N z, NO and Oz. The energy level
scheme for these molecules in the ground state is shown in Fig. 3.1. For N z and
Oz the 1au and lag levels are degenerate in the ground state and all levels up to
the 3aglevel are filled. The doubly degenerate 1ng (or 1nt) orbitals correspond to
the lowest unfilled levels, being empty in N z and half full (two electrons) for O 2 ,
For NO the equivalent of the 1nt orbitals are called the 2n* orbitals and one of
them is singly occupied. Hence N z is a closed shell molecule and both NO and
Oz are open shell molecules and therefore paramagnetic.
The energy levels relevant to the following discussion of the K-shell spectra
of the molecules are shown in Fig.3.11a. For N z we only consider the n*
excitation. According to the dipole selection rule excitation of a spin-down
(spin-up) electron from the 1au level leads to a spin-down (spin-up) electron in
the In: level and both processes are energetically equivalent, leading to only one
n* resonance. The spin-flip transition shown in Fig. 3.11a is dipole forbidden
since the total spin of the 3 n final state is different to that of the 11; initial ground
state. This transition can in fact be observed in ISEELS experiments carried out
under nondipole conditions [3.46] and the energy separation between the two
configurations, arising from a difference in exchange interaction, was found to
be d 1 = 0.82 ± 0.01 eV.
If a spin-up occupation of one of the 2n* orbitals in NO is assumed, only
excitation of a spin-down electron from the 1a (0 Is) or 2a (N Is) orbital to the
half occupied orbital is allowed by the dipole selection rule and the Pauli
principle. Excitation of either a spin-up or spin-down electron is allowed into the
second, empty 2n* orbital. The exchange splitting between the possible three
final states has not been observed and was therefore inferred to be < 1 eV
[3.49]. Ionization of a K-shell electron may lead to two different ionic states
resulting in two different IPs. As shown in Fig. 3.11 b, the two ionic final states
labeled 1 nand 3 n are energetically nondegenerate because of the different spin
coupling and hence exchange interaction in the two states. The exchange
splitting d z has been determined by photoemission to be 1.42 eV for N Is and
0.55 eV for 0 Is excitation [3.47]. Note that for ionization it is customary to
label the final state, by ignoring the photoelectron, as that of the ion left behind.
 3.7 Spin-Dependent Excitations 77

(a) Nitrogen (b) Nitric Oxide

Vacuum __. -__________. -__

---------/j.-:--,- - - - - - - Level

-fL=+=
! I ==<IH== 2,,'
l"g f

1,"
dipole
forbidden

-+t---
I
lau

(c) Oxygen

r
Vacuum Level

'"i

forbidden

I
lau 4+--
Fig. 3.11. (a) Energy level diagram illustrating the origin of the n* resonance in the nitrogen
molecule. The spin-dependent dipole selection rule connects the lu u (N Is) core level and the empty
In: level with conservation of the total spin. Hence from the 1;[ molecular ground state the spin-flip
transition to the 3 [J final state is forbidden but the spin-conserving transition to the I [J final state is
allowed. The energy separation ~I = 0.82 eV has been measured under nondipole conditions [3.46].
(b) In the open shell molecule nitric oxide the occupation of the 2n* orbital by a single electron in
the ground state leads to two different K-shell ionization potentials depending on whether a spin-up
or spin-down electron is excited from the 10' (0 Is) or 20' (N Is) orbital. The exchange splitting ~2 has
been measured by photoemission to be 1.42 eV for N Is and 0.55 eV for 0 Is excitation [3.47]. (c) K-
shell transitions in the paramagnetic O 2 molecule which in its 3;[ ground state has an unpaired
electron in each of the two degenerate In: orbitals. According to Hund's rule, the two spins are
parallel and we shall assume that they are both up. Then excitation of a spin-up electron from the K-
shell to the In:
orbitals is forbidden but excitation of a spin-down electron is allowed, corresponding
to a 3[J final state. As in NO there are two ionization potentials, labeled 2;[ and 4;[, as discussed in
the text. Also, in O 2 there are two 0'* resonances, corresponding to excitations of either a spin-up or
spin-down electron from the K-shell to the 30': orbital.

Relative to the 2II ground state of NO there is thus one electron less in the ionic
final state and this accounts for the change in spin by ± 1/2 between the 2 II
ground state and the 1 II and 3 II excited states. As required by the dipole
selection rule the spin of the total system (ion plus photoelectron) is preserved.
7'ii 3. Symmetry and Molecular Orbitals

Finally, we discuss the particularly interesting case of the O 2 molecule

(Fig.3.11c). In the 3}; ground state the In: orbitals are occupied by two
electrons with parallel spins according to Hund's rule, and for the following
discussion we shall assume that their spins are up. Because of the dipole
selection rule and the Pauli principle only a spin-down electron from the 100u
n:
orbital can therefore be excited into either 1 orbital, giving rise to the 3 II
molecular state. Similar to NO, there are two Is IPs corresponding to excitation
of a spin-up e}; ionic final state) and a spin-down (4}; ionic final state) electron
from the 100u or 10"g orbitals. The corresponding exchange splitting Ll4 has been
determined to be 1.1 eV by photoemission [3.16]. The K -shell spectrum of
oxygen is different from those of N2 and NO in that the transition to the next
higher 30"~ orbital (Fig. 3.1) has a transition energy less than the Is IP [3.50].
For the 10"g --> 30"~ excitation the dipole selection rule only allows the two 3};
final state configurations shown in Fig. 3.l1c, with a difference Ll3 in binding
energy of the 30"~ orbital. Thus the difference in 100g --> 30"~ excitation energy for
the two final state configurations, given by Ll3 - Ll4' corresponds to the splitting
of the two corresponding 0"* resonances in the NEXAFS spectrum. Experiment
shows this splitting to be remarkably large, ~ 3 eV [3.48], as discussed in
Sect. 4.2.8.
In the next chapter we shall give an overview of experimental techniques and
results for K-shell spectra of free molecules and apply the theoretical concepts
discussed above to obtain an understanding of the spectra.
4. Experimental and Calculated K-Shell Spectra
of Simple Free Molecules

Here an overview is given of the spectral features that are encountered in K-

shell excitation spectra of simple gas phase molecules. Experimental results ob-
tained by the inner shell electron energy loss, or ISEELS, technique - which
is discussed first - are compared to those obtained by different theoretical
techniques.

4.1 Experimental Methods: The ISEELS Techniques

Although historically X-ray absorption spectroscopy has been the technique of

choice for the study of inner shell excitation processes in matter, our detailed
understanding of the K-shell spectra of low-Z molecules is largely due to a
different technique, namely inner shell electron energy loss spectroscopy, or
ISEELS [4.1, 2]. For example, this technique which closely approximates X-ray
absorption spectroscopy has been used to study the carbon K-shell spectra of
more than one hundred molecules [4.2] while only a few such studies have been
carried out by means of X-ray absorption [4.3-13]. A summary of the early X-
ray absorption and some of the early ISEELS work has been given in a review
by Koch and Sonntag [4.14].
One reason for the dominance of IS EELS in investigating molecules lies in
the long-time unavailability of highly monochromatic, intense tunable photon
radiation in the 250-1000eV range. Even with the utilization of synchrotron
radiation in the early 1970s, problems with beam line optics impeded extensive
work in this spectral range [4.15]. Another important reason is the experimental
convenience of ISEELS measurements. ISEELS spectrometers are relatively
inexpensive and home based, which is why they have been called the "poor
man's synchrotron". Other factors are their extremely high and energy-inde-
pendent energy resolution ( ~ 50 me V) and the fact that ISEELS measurements
do not suffer from saturation effects in the recorded spectra which plagued early
X-ray absorption studies, e.g., the pioneering N2 K-shell work by Nakamura et
al. [4.16] as discussed by Connerade et al. [4.17]. The resolution capabilities of
ISEELS at the C K-edge of CO and the N K-edge of N2 are demonstrated in
Fig. 4.1, which shows vibrational fine structure in the Is -+ n* transitions of the
molecules [4.18-20]. Similar resolution has only very recently been achieved
80 4. Experimental and Calculated K-Shell Spectra of Simple Free Molecules

Vibrational Structure In fT* Resonance Fig. 4.1. Vibrational structure of the

Is -+ n* transition recorded with high
1.0
N2 resolution ISEELS for N 2 [4.19] and CO
Eo = 2.5 keY (C K-shell) [4.20] gas. Eo denotes the
6E = 90 meV primary electron beam energy and I'lE
0.8 the instrumental energy resolution. The
N2 spectrum is least-squares fitted with
six Lorentzians
0.8

~ 0.4&.....1!~c...
c:

.e'" 400 401 402

~ ;-~-r~~~~--~-.--~~~~
~
'iii
~1.4
..:- CO
.s Eo = 1.5 keY
6E = 55 meV
1.0

0.6

0.2 ) \ . ' \.....

o I:....:---::::;;:....I.--.J..~::;:::::::::::::::.J
287 288
Energy Loss (eV)

with X-ray absorption spectroscopy [4.21, 22], ten years after the IS EELS
spectra in Fig. 4.1 were recorded. We will briefly describe the ISEELS technique.
The energy loss of electrons passing through gases was studied as early as
1914 by Franck and Hertz [4.23]. These experiments are often used in physics
textbooks to explain the different nature of electron versus photon interactions
with atoms. In collisions, energetic electrons (a few keY) can lose any fraction of
their energy through electronic excitations of atoms or molecules while the
interaction of photons with matter (except for energies above about 100keV
when incoherent scattering becomes important) is characterized by complete
loss of energy, i.e., absorption. The resonant character of X-ray absorption is the
reason for saturation effects in the recorded K-shell structures at high molecular
densities [4.17] while such effects are nonexistent in the nonresonant ISEELS
measurements. Ironically, Franck and Hertz's experiments, which demonstrated
the difference between X-ray and electron excitations of atoms, are also the basis
for application of electron energy loss spectroscopy in a manner equivalent to
photon absorption.
In 1930 Bethe [4.24] showed that under certain conditions the electron
energy-loss cross section can be directly related to the X-ray or optical absorp-
tion cross section, where the energy loss E) of the electron during the collision
 4.1 Experimental Methods: The ISEELS Techniques 81

event is equivalent to the photon energy. The latter equivalence is easy to

understand since the energy required to excite an atom from state Ii) to state
<II is furnished by energy loss in one case and photon absorption in the other. If
the energy loss of the electron during the collision event is small compared to its
kinetic energy, the interaction between the electron and the atom can be treated
in lowest order and the first Born approximation can be used. In this case the
number of electrons that have lost an energy E) in a collision with an atom and
are scattered in a direction characterized by the momentum qf = qi - Q. where
Q is the momentum transfer, is proportional to the double-differential cross
section [4.24, 25]

(4.1)

where I(Q, E) is a Q- and E)-dependent function [4.25, 26] and the summation
is over all electrons with coordinates rj in the target atom. In the limit Q' r ~ 1,
where r is the radius of the initial core state, the exponential factor in (4.1) can be
simplified by expansion in a power series

(4.2)

Because the states Ii) and <II are orthogonal, the matrix element ofthe first
term in the series vanishes. The second term yields the familiar dipole matrix
element, the third term the quadrupole matrix element and so on. Note that the
dipole approximation in X-ray absorption corresponds to approximating the
exponential term in (2.7) to 1, the first term of the power series, while in IS EELS
the exponential term in (4.2) is approximated by the first two terms 1 + i Q' r. If
we choose our experimental conditions such that the momentum transfer Q is
small, the dipole term will dominate over the higher multipole terms. Further-
more, if we define r = Ljrj and integrate over the finite angular acceptance of
the spectrometer up to a maximum angle Om from the incident beam direction,
we obtain [4.25-27]

(4.3)

where Eo is the incident beam energy and eQ is a unit vector in the direction of
the momentum transfer Q. It is interesting to compare the above expression to
that governing X-ray absorption which, according to (2.8. 11), can be written as
[4.26,28],

(4.4)

where q is the wave vector magnitude of the photoelectron and eE is a unit vector
in the direction of the electric field vector E of the X-rays. Thus in the limit of
small momentum transfer, ISEELS spectra are dominated by dipole transitions
where the Q vector takes the role of the E vector in X-ray absorption. The
"polarization" dependence of ISEELS has in fact been utilized to study the
82 4. Experimental and Calculated K-Shell Spectra of Simple Free Molecules

anisotropy of solids [4.26,29-31], and it has also been used to probe structural
and dynamic anisotropies of surfaces [4.32], and the orientation of chemisorbed
molecules [4.33, 34].
Experimentally the ISEELS cross section dUe/dE) (units: cm 2 /eV) and X-ray
absorption cross section U x (units: cm 2 = 10 24 barn) are measured by moni-
toring the transmission of an electron or X-ray beam through a gas character-
ized by its volume density nv (atoms/cm 3 ) and the X-ray path length t through
the gas. If we denote by 10 , the incident photon or electron flux density, [e.g.,
photons/(scm 2 )] and by Ao the area of the sample exposed to the beam (cm 2 ),
the transmitted number of photons N ph is given by the familiar expression

(4.5)

The product nvux = J.i.x is called the linear X-ray absorption coefficient. In
ISEELS the incident beam has an energy Eo and the number of electrons
dNe/dE) having lost an energy E) through core excitation in the gas in given by

(4.6)

Here we have assumed that the sample density is kept sufficiently low that
multiple scattering events are negligible [4.35]. As discussed in detail by Inokuti
[4.25] who elucidated the physical concepts of the Bethe theory, the ISEELS
cross section per unit energy loss in the case of forward scattering (observation
along the incident beam direction with vanishing angular spectrometer accept-
ance) is even quantitatively related to the X-ray absorption cross section Ux' In
this case, corresponding to Q = 0, one obtains [4.25]

dUe -3
-d = BEo(E) uX (4.7)
E)
,

where the constant B is given by B = 8mc 2 (e 2 /hc). Note that the quantity in
parentheses is the dimensionless fine structure constant. Because of the finite
angular acceptance of ISEELS spectrometers, in practice, a range of Q vectors is
measured and the cross section dUe/dE) and X-ray absorption cross section U x
differ by a factor (E)-n with 2 ::; n ::; 3. Procedures for converting ISEELS
spectra recorded at finite spectrometer acceptance angles into absolute X-ray
absorption cross sections ha~e been discussed in the literature [4.26, 27] and
used to derive absolute transition intensities for free molecules [4.36, 37].
Equation (4.7) tells us that ISEELS is best suited to study excitations of
relatively low energy since its cross section drops off with the third power of E).
In practice, this limits ISEELS to the study of inner shells with binding energies
in the range ~ 1000eV.
Modern ISEELS spectroscopy of atoms and molecules was pioneered in the
early 1970s by Van der Wiel [4.38] and Brion [4.39] who showed that it was
possible to carry out measurements close to the optical limit by using sufficiently
 4.2 Characteristic Resonances in K-Shell Spectra 83

high electron beam energies and a forward scattering geometry. It is interesting

to note that ISEELS can also be applied to solids using thin film samples and
beam energies of l00keV or more in order to avoid multiple inelastic scattering
events in the sample [4.40,41]. A comprehensive review ofISEELS of solids has
been given by Egerton [4.41]. Surface ISEELS studies, which are typically
carried out in reflection geometry and with primary beam energies of a few ke V,
have been reviewed by De Crescenzi [4.42]. Such studies have investigated clean
surfaces [4.43] and metallic overlayers [4.44], as well as atomic [4.45] and
molecular [4.33, 34] adsorbates.
The instrumentation for ISEELS of free atoms and molecules has been
discussed by several authors [4.1, 20, 46-48]. Spectra are typically recorded with
electron energies Eo ~ 3 keY and a ±0.5° angular acceptance of the electron
energy loss analyzer around the direction of the incident beam. This corres-
ponds to a maximum momentum transfer of Q = 2.4 A- 1 at the oxygen K -edge
(530eV). Using the oxygen (Z = 8) K-shell diameter r ~ 2ao/Z = 0.13 A, where
ao = 0.529 A is the Bohr radius, the product Qr = 0.32 A indicates that the
dipole term in (4.2) is only a factor 6 larger than the quadrupole term.
Experimental studies, however, show excellent agreement with X-ray absorp-
tion, indicating that the dipole approximation holds better than expected. A
possible explanation is the relative weakness of the quadrupole matrix elements
[4.49]. In a few cases quadrupole transitions have been observed, the most
dramatic case being for PCl 3 [4.50].
We shall go on to discuss K-shell spectra offree molecules obtained with the
ISEELS technique and in a few cases with X-ray absorption and compare them
to spectra calculated with the XIX-MS and/or ST-MO techniques. The purpose
of this chapter is the understanding of the major characteristics of molecular K-
shell spectra. The basis for this understanding is provided by the spectra of
simple diatomics, pseudo-diatomics or other small molecules and we shall
therefore restrict our discussion here to those systems. Spectra of larger mole-
cules are discussed in Chap. 6 in conjunction with those of macromolecules and
polymers.

4.2 Characteristic Resonances in K-Shell Spectra

4.2.1 Overview
The K -shell spectra of atoms and molecules contain a variety of pronounced
resonances whic,h correspond to electronic transitions of a K -shell electron to
states near the vacuum level and therefore fall at an excitation energy close to
the IP. The purpose of this section is to survey the different kind of resonances
typically encountered in molecular K-shell spectra. To simplify matters we only
consider "simple" molecules, either diatomics or pseudo-diatomics (ignoring
hydrogens), or larger molecules where there is little interaction between adjacent
84 4. Experimental and Calculated K-Shell Spectra of Simple Free Molecules

bonds. Thus we ignore all molecules where first order bond-bond interactions
(Sects. 3.4 and 3.5) between second row atoms are important, as in systems with
n and/or a conjugation. Also, second order bond-bond interactions must be
weak. Therefore we do not consider cases where the antibonding orbitals
associated with different neighbor bonds are similar in energy, e.g., C-C and
C-O a* or C = C and C = 0 n* orbitals, respectively. This selection allows us to
lay the foundation for the understanding of the spectra of complex free mole-
cules, as well as chemisorbed or polymeric molecules, which are discussed in
terms of the spectra of diatomic building blocks in Chap. 6.
The effective molecular potential and different types of final states for an
atom and a diatomic molecule respectively are depicted in Fig. 4.2. In construct-
ing this figure we have drawn from the theory discussed in Chap. 2. The plotted
potential for the diatomic molecule differs in shape from the muffin-tin potential
shown in Fig. 2.7 in that it assumes positive values at the periphery of the
molecule, i.e., contains a potential barrier. The barrier is due to an additional
centrifugal term 1(1 + l)h 2/(2mr2) in the molecular (or atomic) potential which
arises when the Schrodinger equation is written in spherical coordinates. Thus
the radial part of the wave equation written in the center-of-mass coordinate
system of the molecule contains an "effective potential" which is the sum of the
Coulomb and exchange potentials (2.58) and a centrifugal potential. The poten-
tial barrier term depends on angular momentum 1and for K-shell excitations of
atoms is small because the excited photoelectron has angular momentum 1 = 1.
For K-shell excitation of molecules, however, the final state wavefunction is only
of 1 = 1 nature in the coordinate system of the excited atom. In the center-of-
mass molecular coordinate system all I-values are allowed (Sect. 2.7.4 and
Appendix A) and therefore the potential barrier may be appreciable.
For a closed shell atom in its ground state, say a noble gas atom, the
Schrodinger equation predicts empty Rydberg states just below the vacuum
level (Ev) and a continuum of empty states above it. The same picture applies for
the core excited atom; the energies of the electronic states are however shifted.
Hence we expect the K-shell excitation spectrum to resemble that shown at the
top left of Fig. 4.2. Here we have simply assumed that transitions of the Is core
electron to all empty states are allowed and ignored all multi-electron excita-
tions. For a diatomic molecule we also have Rydberg states below, and con-
tinuum states above, Ev' In addition, there are unfilled or empty molecular
orbitals. As discussed in Sect. 3.1, it is convenient to simply label the MOs in
terms of a or n symmetry and denote unfilled MOs- by an asterisk. As illustrated
by Fig. 2.5, the lowest unoccupied MO (LUMO) for a diatomic is usually a n*
orbital with a a* orbital at higher energy. For the neutral molecule these states
typically lie above the vacuum level but the n* state is pulled below Ev by the
electron-hole Coulomb interaction (Fig. 2.4). This yields the schematic effective
potential and energy level diagram shown at the bottom right of Fig. 4.2 and the
K-shell spectrum shown above it. Let us now compare these simple concepts to
experimentally observed spectra.
 4.2 Characteristic Resonances in K-Shell Spectra 85

Rydberg tr-

IP Photon Energy IP Photon Energy

Rydberg
States

y X
Fig. 4.2. Schematic potentials (bottom) and K-shell spectra (top) of atoms and diatomic molecules.
The effective potentials include the centrifugal term [ oc 1(1 + 1)/r 2 ] , which is small for K-shell
excitation of an atom (I = I) but may be large for K-shell excitation ofa molecule because relative to
the center of the molecule large I-values may dominate in the wave function of the excited electron.
For the diatomic, the centrifugal term gives rise to the indicated barrier, which separates an inner
well near the atomic positions from a shallower outer well. The inner well contains all core and
valence atomic or molecular orbitals. The wavefunctions of the lowest energy Rydberg orbitals may
also be largely confined to the inner well but lie almost entirely in the outer well for the higher
members of the series, i.e., those close to the vacuum level. Unfilled MOs are indicated by an asterisk
label (e.g. 0'*). Resonances in K-shell spectra arise from electronic transitions from a Is initial state to
Rydberg or unfilled-MO final states. At the IP, corresponding to the threshold for transitions to
continuum states, a step-like increase in X-ray absorption is expected. These effects lead to the
characteristic features of atomic and molecular K-shell spectra schematically shown in the upper
part of the figure. In addition to these "one-electron" features other structures arising from "multi-
electron" transitions may be observed

We have already encountered the K-shell spectrum of the simplest case,

namely a noble gas atom, in Fig. 2.1. The spectra are characterized by a few
sharp resonances approximately 2-6 eV below the IP followed by a step-like
increase in absorption around 2 eV below the IP. To illustrate how this "atomic"
spectrum develops into a "molecular" one we show in Fig. 4.3 the K-shell
86 4. Experimental and Calculated K-Shell Spectra of Simple Free Molecules

:r···"3f·······,····· ··~;···l
;~t '''2 NH, 1
i~I N2
H
.j
~1~1 -10 o 10 20
Energy from IP (eV)

Fig. 4.3. ISEELS K-shell spectra of neon (Ne) [4.51. 52]. ammonia (NH3) [4.53]. hydrazine (N 2H 4)
[4.51]. and nitrogen (N 2) [4.51. 54]. All spectra are aligned at the Is IPs [4.55]. The figure illustrates
the increasing number of resonances introduced by additional bonds: The Ne spectrum exhibits a
pronounced Rydberg resonance", 3eV below the IP. NH3 exhibits two pronounced bound state
resonances which are stronger relative to the continuum step than in Ne because of N-H valence
orbital admixtures to the Rydberg states. Note that Ne is the united atom ofNH 3. N2H4 exhibits an
additional N-N single bond (1* resonance close to the IP. Triple bonded N2 shows a pronounced n*
bound state resonance and a (1* shape resonance in the continuum around geV above the IP. The
structure around 5eV above the IP in N2 is a multi-electron resonance

spectrum of Ne [4.51, 52] and in comparison that of isoelectronic NH3 [4.51,

53]. The spectra look surprisingly similar, the main difference being the greater
intensity of the discrete transitions. This can be attributed to the fact that the
wavefunctions of the final states in NH3 are no longer pure Rydberg orbitals but
contain an admixture of hydrogen-derived valence orbitals [4.56, 57].
In contrast, the K-shell spectrum of the hydrazine (N 2H 4) molecule [4.51]
(Fig. 4.3) exhibits a new resonance around 1 eV below the IP. In hydrazine two
NH2 groups are bonded together by a N-N single bond and the additional
resonance arises from a transition to the N-N antibonding u* orbital, which is
unoccupied. Also note that the vertical scale in Fig. 4.3 is in absolute oscillator
strength units and the overall absorption step or edge jump is a factor of 2 larger
in N2H4 than in NH 3. This is the result ofthe fsum rule (2.15), which links the
oscillator strength to the number of electrons in the atom or molecule. More
precisely, it arises from the approximate fsum rule for the K-subshell as
discussed in Sect. 2.1.2. It also appears that the N-N u* resonance takes away
oscillator strength from the N-H valence/Rydberg resonances since these are
 4.2 Characteristic Resonances in K-Shell Spectra 87

less pronounced relative to the continuum cross-section than for NH 3 . This,

again, is a consequence of the approximate fsum rule for the K-shell, stating
that the integrated oscillator strength is a constant.
Finally, at the bottom of Fig. 4.3 we show the spectrum of the nitrogen
molecule [4.51, 54] which is linked by two N- N n bonds and one a bond, i.e., a
triple bond [4.58]. Indeed, this bonding situation is directly reflected by its K-
shell spectrum. The lowest energy resonance around 9 eV below the IP arises
from a transition of the is electron to the N-N anti bonding in: orbital, and the
highest energy resonance around 9 eV above the IP is due to a transition to the
N-N a:
antibonding orbital [4.54]. The weak structures below the IP are
Rydberg resonances which, in general, can be identified by their characteristic
term values, i.e., their separation from the IP [4.56]. The structure near 5eV
above the IP is a multi-electron excitation feature [4.59- 63]. Note that without
this structure the N 2 spectrum closely resembles the schematic spectrum in
Fig. 4.2.
The origin of the molecular resonances shown in Fig. 4.3 is confirmed by the
results of Xa-MS calculations by Wurth and Stohr, shown in Fig. 4.4 [4.64].
These calculations were performed using the transition state method, choosing
the atomic sphere radii to match calculated and experimental IPs. In Fig. 4.4 we
have plotted both experiment and theory in absolute cross section units of Mb
(= 10- 18 cm 2). The overall agreement between theory and experiment is re-
markably good. Except for the multi-electron peak in the N2 spectrum at 5 eV

Experiment Theory

4 (a) 5 2e' (b)

N- H' 4
3
2 3
_ 2
1 NH3 .c
D NH3
~ 1

~~I
j~ N, H,
1
!1!
U 0

i
4
3 o·
2
xV. I
1
0
- 10 0 10 20 - 10 0 10 20
Energy from IP (eV) Energy from IP (eV)

'''9
Fig. 4.4. Comparison of the molecular K-shell spectra of NH 3 , N 2H 4 , and N2 taken from Fig. 4.3
to those calculated by means of the Xa-MS technique [4.64]. Note that the experimental intensities
of Fig. 4.3 have been converted to cross section units of Mb, according to (2.12). Between the spectra
we have depicted those molecular orbitals, taken from [4.58], which are associated with specific
resonances in the spectra. The orbitals and corresponding resonances in the calculated spectra are
labeled by the irreducible representations of the MOs
88 4. Experimental and Calculated K-Shell Spectra of Simple Free Molecules

above the IP, all experimental features are accounted for. This indicates that
such one-electron calculations can be used to assign all major resonances and
that features not reproduced by the calculations are most likely of multi-electron
character. To illustrate the origin of specific resonances we have also shown in
Fig. 4.4 orbital contours of unfilled MOs associated with the resonances. The
pictures are from [4.58] and are labeled with their irreducible representations.
The same labels are used for the resonances in the calculated spectra.
Before we discuss the main resonances encountered in K -shell excitation
spectra in more detail, it should be pointed out that similar resonance features
are also observed in the excitation spectra of the valence shells [4.65, 66].
However, the particularly simple symmetry and the localized nature of the Is
initial state greatly favors the study of the K -shell. As pointed out by Dehmer et
al. [4.67], valence shell spectra are complicated by the delocalized nature of the
valence-hole state leading to more complicated electron correlation and screen-
ing effects and strong particle-hole interactions, by a greater energy dependence
of the dipole matrix element, and by strong continuum--continuum coupling
between nearly degenerate ionization channels. These complications obscure the
intensities and energy positions of the resonances. In contrast, K-shell spectra
are less complicated and their interpretation can be guided by simple, general
rules, to be discussed.

4.2.2 7l'* Resonances

In the spectrum ofN 2 (Fig. 4.3) several sharp peaks are observed below the Is IP
(Fig. 4.2). The most pronounced resonance by far is the lowest energy peak,
which corresponds to a transition to a n* anti bonding orbital of the molecule. In
the following we shall refer to such commonly observed Is ~ n* transitions as
n* resonances. In all known K-shell spectra of low-Z molecules the n* reson-
ance, if present, is the lowest energy structure and its energy position falls below
the Is IP. In the ground state the final state valence orbital associated with such
transitions can be empty (e.g., CO) or partially filled (e.g., NO). For a molecule in
its ground state empty states lie above, and partly filled states below, the vacuum
level. In the core excited molecule there is an upward (smaller binding energy)
relaxation shift of the Is orbital and a downward shift of the outer "optical"
orbitals because of the increased attractive Coulomb potential created by the
core hole [4.68]. The Coulombic shift of the outer orbital results in a transition
energy of the n* resonance which is less than the Is IP. In fact, CO with a C Is
core hole and N2 with a N Is hole and an electron in the n* orbital resemble NO
in the equivalent core approximation and it is therefore not surprizing that the
n* resonances for N 2 and CO lie below the IP by nearly the same amount
(~9 eV) as the partially filled n* orbital for neutral NO lies below the vacuum
level, as discussed in Sect. 2.4.2.
A n* resonance is only observed for molecules with n bonding. For example,
experimental and calculated [4.64] spectra for molecules with C-O bonds
shown in Fig. 4.5 exhibit a n* [Link] for triple and double C-O bonds as in
 4.2 Characteristic Resonances in K-Shell Spectra 89

Experiment

J J
C K-edge OK-edge

(a) (c)
u· u·
CO
x- x3

1
~
c:
'0 I
::l IP
IP
€
.!!!.
~
on
c: [Link]
~

[Link]

310 320 530 540 550 560

Energy Loss (eV)

Theory
C K·edge o K·edge

J .~
(b) >T" (d)
0"

i
0"

xV. )(V2 :
CO , I

iii
.'c:" /
I
I
I
>T*
I - I

::l >T*

P
I
~
c:
I
!!
I [Link]
.!:

[Link]
280 290 300 310 320 530 540 550 560
Excitation Energy (eV)

Fig. 4.5. Top: Experimental ISEELS spectra above the C and OK-edges for carbon monoxide
(C=O) [4.51, 54], formaldehyde (H 2 C=O) [4.51, 69], and methanol (H3C-OH) [4.37, 51, 53].
Bottom: Corresponding K -shell spectra calculated by means of the Xa-MS technique [4.64] for the
same molecules. The Is IPs determined by photoemission (top) [4.55] and calculated (bottom) are
indicated by vertical lines. Note that no 71:* resonance exists for single-bonded CH 30H. The strong
energy dependence of the (1* resonance can be correlated with the change in C-O bond length:
1.128..\ for CO, 1.209..\ for H 2 CO, and 1.425..\ for CH 30H [4.70]

C=O [4.51, 54] and H 2 C=O (formaldehyde) [4.51, 69] but not for single
bonded H3C-OH (methanol) [4.37, 51, 53]. The natural width (in the absence of
instrumental broadening) of the resonances is determined by the lifetime of the
excited state, see (2.16), and the vibrational motion of the molecule. In the n*
resonance, the final state lifetime of the free molecule is determined by the decay
of the core hole, which predominantly proceeds via autoionization, i.e., deexcit-
ation of the excited electron in the n* state to the K-shell and simultaneous
90 4. Experimental and Calculated K-Shell Spectra of Simple Free Molecules

emission of a valence electron [4.71]. The n* resonance lifetime width for N2

and for the C K -edge in CO is extremely small (::: 0.1 eV) and this allows
observation of the vibrational energy levels of the electronic final state with
intensities determined by the appropriate Franck-Condon factors (Fig. 4.1)
[4.72]. Within a series of molecules containing the same atoms, the intensity of
the n* resonance changes with the bond order between the atoms. This is
illustrated by Fig. 4.5, where the intensity of the n* resonance relative to the
absorption continuum changes between double bonded H 2C = 0 and triple
bonded C == o. Quantitative measurements [4.27, 73] show a decrease in the n*
intensity by a factor of 2.3 at the C K-edge and an increase by a factor of 1.3 at
the 0 K-edge between CO and H 2CO, respectively. This indicates that at the C
K -edge the n* resonance loses oscillator strength to the resonances associated
with C-H bonds (see below).

4.2.3 Rydberg and Mixed Valence/Rydberg Resonances

Between the n* resonance and the IP several sharp but weak resonances can be
observed (Figs. 4.3, 5) which correspond to excitations to Rydberg orbitals or, in
the presence of bonds to hydrogen atoms, to a mixture of Rydberg and
hydrogen-derived antibonding orbitals of the same symmetry [4.56, 74]. The
resonances merge into a continuous step-like feature about 2 eV below the IP as
expected from a Rydberg series of states. Figure 4.5 shows that the intensity of
these sharp resonances relative to the continuum absorption at the highest
energy is weakest for CO and increases with the addition of hydrogen atoms in
H 2C = 0 and H3C-OH. Furthermore, the intensity of these resonances is
stronger for the C K-edge excitation than for the 0 K-edge excitation. Rydberg
features are generally weaker in the higher energy edges because of the decreased
size of the Is orbital and hence the smaller spatial overlap with the Rydberg
orbital. In H 2CO, another reason for the reduction of the corresponding
resonance in the 0 K -edge relative to the C K -edge spectra stems from the
presence of C-H valence orbitals and the absence of O-H valence orbitals. The
weak intensity of the peaks for CO is associated with the large spatial extent of
Rydberg orbitals, which have most of their orbital density at the periphery of the
molecule, in the outer well (Fig. 4.2). Mixing of the Rydberg orbitals with
hydrogen-derived valence orbitals increases the intensity of the corresponding
resonance because of the more compact nature of the valence orbitals [4.75, 76].
The correlation between Rydberg and hydrogen-derived molecular orbitals
can be well illustrated for the simple molecules methane (CH 4 ), ammonia (NH 3),
water (H 20) and hydrogen fluoride (HF) whose K-shell excitation spectra [4.53,
77] are shown in Fig. 4.6. The spectra are quite similar and exhibit structures
primarily below the respective Is IPs, as expected. 1 We have denoted the two

1 Previously, weak structures in the continuum, in the range 10-20eV above the IP, have been
assigned in [4.79] to u* shape resonances associated with hydrogen bonds. We now believe that this
assignment is probably incorrect and that the structures more likely arise from shake-up continua.
 4.2 Characteristic Resonances in K-Shell Spectra 91

40"*

-10 0 10
Energy from IP (eV)
Fig. 4.6. ISEELS spectra of the isoelectronic molecules methane (CH 4 ), ammonia (NH 3 ), water
(H 2 0) [4.53] and hydrogen fluoride (HF) [4.77). In all cases the IP has been subtracted from the
measured electron loss energy, in order to compare the spectra on the same energy scale. Resonances
A and B correspond to transitions to the hydrogen-derived anti bonding molecular orbitals shown
on the right taken from [4.58). Peaks A correspond to transitions to a!, and for HF to the 417*, final
states, and peaks B are associated with (from top to bottom) the 2t1, 2e*, and 2b! MOs. These
orbitals are strongly mixed with Rydberg orbitals of the same symmetry but for K -shell excitations
the valence character of the final state largely determines the resonance intensity [4.78]

most prominent resonances as A and B. Originally these resonances were

attributed by Wight and Brion mainly to Rydberg states associated with 38 and
3p atomic final states [4.53], although it was pointed out that the 3p state for
NH3 was known to have appreciable anti bonding character. Later, in their
analysis of the HF spectrum, Hitchcock and Brion [4.77] pointed out that the
mixing of Rydberg and hydrogen-derived valence-type orbitals is a more general
phenomenon, and specifically associated the lowest energy resonance in HF
with the 4u* H-F anti bonding orbital (Fig. 4.6) [4.58]. In a direct comparison of
92 4. Experimental and Calculated K-SheJl Spectra of Simple Free Molecules

K-shell spectra for CH 4 , NH 3, and H 2 0 with that of the united atom Ne

(Fig. 4.3), Akimov et al. [4.57] attributed the shift of resonances A and B in
Fig. 4.6 to valence (electronegativity) effects and concluded that the states must
be of mixed valence/Rydberg type. This was later supported by ab initio
calculations by Chang et al. [4.80].
Recently it has become apparent from the detailed inspection of K-shell
spectra of cyclic [4.78] and linear [4.81, 82] hydrocarbons that many "Rydberg"
resonances observed over the years in hydrocarbons and molecules with C-H
bonds are in fact better described as mixed Rydberg/valence resonances, since
for K-shell excitations the peak intensities are often determined by the valence-
like rather than the Rydberg-like nature of the final state. Such findings lead to
the correspondence between resonances A and B in Fig. 4.6 with the hydrogen-
derived anti bonding orbitals discussed in Sect. 3.2.2 (compare Fig. 3.3) and
shown on the right side of the figure. Resonances A correspond to the valence
orbitals with a 1 symmetry mixed with the 3s a 1 Rydberg orbitals, or in the case
of HF to the 4<1* orbital. For CH 4 the Is (lad -+ 3ar transition is symmetry
forbidden and becomes allowed only through Herzberg-Teller vibronic coup-
ling [4.83]. Resonances B are associated with the 2t 2, 2e, and 2b 1 antibonding
orbitals in CH 4 , NH3 and H 2 0, which are mixed with the 3pt2' 3pe, and 3pb 1
Rydberg states, respectively. Note that for the core excited final state the empty
MOs are pulled below Ev by the effective Z + 1 Coulomb potential of the
equivalent core and can therefore mix more extensively with the Rydberg
orbitals. Thus, to a large degree the mixing is a final state effect. In addition, the
character of the unfilled orbital sampled is dependent on the spectroscopic
technique. For K-shell excitation, it is the small-R region of the Is core which
contributes the most. As noted by Mulliken [4.84], a MO is more valence
at small R and more Rydberg at large R, an effect which has been called
"Rydbergization".
More evidence for the valence nature of the final states associated with the
resonances in Fig. 4.6 comes from H + yield spectra of condensed and chemi-
sorbed water [4.85]. Here the enhanced H + yield at the first resonance position
(peak A) and its angular dependence were taken as direct evidence for the
valence character of the associated state. The correspondence between the
resonances and hydrogen-derived valence orbitals in Fig. 4.6 has important
consequences, since for chemisorbed molecules resonances A and B should
exhibit a different polarization dependence (with the exception of CH 4 ) and may
therefore be used to determine the orientation of the molecules on the surface 2 •
The survival of the Rydberg/valence resonances upon chemisorption may
yield interesting information regarding the strength of the chemisorption bond
for chemisorbed molecules. For strongly chemisorbed molecules one would

2 NEXAFS spectra of chemisorbed NH3 on Ni(J 10), see [Ref. 4.86, Fig. 3], reveal resonances which
were attributed to Rydberg transitions. The observed resonances are better described as transitions
to 4a l u* and the 2e n* N-H valence orbitals
 4.2 Characteristic Resonances in K-Shell Spectra 93

expect pure Rydberg resonances to be quenched upon chemisorption. In con-

trast, hydrogen-derived resonances are expected to survive the chemisorption
process because of their more localized nature, similar to n* and 0'* resonances.
Finally, C-H bond related resonances play an important role in the K-shell
spectra of hydrocarbons (Sect. 4.2.7) and especially in the spectra of polymeric
hydrocarbon chains as discussed in Chap. 6.

4.2.4 0'* Shape Resonances

Above the Is IP, the K-shell spectrum ofN2 and the C K-edge in CO exhibit two
resonances of which only the broader, higher energy one is observed for the 0
K -edge for CO (Fig. 4.5). The lower energy structure has been assigned to multi-
electron excitations associated with the prominent Is -+ n* transition [4.60-63,
87], while the highest energy peak is a so-called 0'* shape resonance [4.59, 88].
Shape resonances are one of the intriguing phenomena associated with molecu-
lar valence and core excitation spectra and the name arises from the idea [4.89,
90] that the excited state is stabilized against immediate decay by a hump in the
potential shape as indicated in Fig. 4.2. In all documented cases the potential
barrier arises from the centrifugal part of the potential and its shape and height
depend on the angular momentum of the final electron state [4.91]. Therefore
shape resonances are associated with particular I components of the electronic
wavefunction and these components are trapped only in certain directions, e.g.,
along the internuclear axis for the 0'* shape resonance.
Recently Natoli [4.92] has questioned the necessity of a potential barrier for
the existence of a continuum resonance and suggested that they should be
viewed more generally as arising from multiple scattering processes of the
photoelectron by the atomic centers. In the potential barrier model, the n*
resonance might be viewed as a "shape resonance below threshold" where the
wavefunction is trapped by an impermeable barrier perpendicular to the inter-
nuclear axis. However, this terminology has been criticized by Schwarz et al.
[4.93], who argue that resonances below and above the IP are of different nature
and suggest the name Feshbach resonances for the structures below the IP. This
terminology is based on that traditionally used in the area oflow energy electron
scattering, as reviewed by Allan [4.66].
Rather than using a scattering picture for the description of the highest
energy resonance in the N 2 spectrum in Fig. 4.3, the resonance can also be
explained in a molecular orbital picture. As discussed in detail by Sheehy et al.
[4.94], the molecular orbital picture naturally yields states of enhanced ampli-
tude on the molecule which lie above the vacuum level without specifically
employing a potential barrier concept. In this picture the 0'* shape resonance
can be described as a two step one-electron process where the K-shell electron is
first excited to a virtual molecular orbital of 0' symmetry, followed by the
emission of a photoelectron [4.95-98]. Examples of such M 0 final states are the
30': and 60'* MOs for N2 and CO shown in Fig. 2.5 or the 60'* MO for NO
pictured in Fig. 2.8. Because of the insignificance of the potential barrier concept
94 4. Experimental and Calculated K-Shell Spectra of Simple Free Molecules

and therefore the "shape" of the potential for the existence of above-threshold
resonances in the MO description, we shall below refer to u* shape resonances
also simply as u* resonances.
The energy width of the u* resonance is related to the lifetime of the quasi-
bound electronic state. Because of the increasing decay probability of the
electron to continuum states, 0'* resonances become broader the higher they lie
in the continuum. Their asymmetric line shape with a tailing toward higher
energy is readily understood in the potential barrier picture emerging from XIX-
MS calculations. Since the probability for tunnelling through the barrier in-
creases with the kinetic energy of the photoelectron, the resonance shape is more
peaked at lower energy with a high energy tail. In another picture the asym-
metry can be understood in analogy to the "giant resonance" line shape [4.99],
which arises quite generally from the interaction of an electron with a potential
well. In particular, the giant resonance line shape is not only asymmetric but
shows dispersion on the high energy side such that it resembles an asymmetric
Gaussian profile with an underlying step function. The line shapes of the near
edge resonances are discussed in more detail in Chap. 7.
Furthermore, 0'* resonances are asymmetrically broadened by the vibra-
tional motion of atoms in the molecule [4.100]. This is shown in Fig. 4.7 for the
0'* resonance of the N2 molecule observed in the excitation of the 30'g inner
valence shell. For variation in intranuclear distance spanning the range of
ground state vibrational amplitude from 1.23 A to 0.965 A, the resonance
position shifts from about 8 eV to 24 eV. Since the electronic excitation is fast
compared to the nuclear motion the X-ray absorption spectrum is a weighted

20 ::_ R = 1.230A
:0-
:::?!
~15
b
c:
o
~ 10
Q)
(J)

~ 5
e
()
t"'~iriiIii~;;:

o~----~----~----~----~
o 10 20 30 40
hv-IP (eV)
Fig. 4.7. Cross section for photoionization of the 30'g valence level ofN2 (binding energy - 16eV)
in the excitation region of the 0'. shape resonance [4.100]. Calculations were carried out as a
function of the internuclear molecular distance R over a range spanning the ground state vibrational
amplitude. The position, strength and width are found to be strong functions of R. The solid curve
corresponds to a summation over the vibrational motions in the ground state and its shape exhibits
an asymmetry which distinguishes it from the resonance shape calculated for R fixed at the
eqUilibrium value 1.095 A (central dashed curve)
 4.2 Characteristic Resonances in K-Shell Spectra 95

average over the distances allowed in the ground state of the molecule. The R
dependence of the resonance position arises from the fact that 0'* orbitals are
directed along the internuclear axis between two atoms, as discussed below, and
it is therefore absent for n* resonances. The distance dependence of shape
resonances has been elegantly measured by vibrationally resolved partial photo-
ionization cross sections of the final ion. Examples are discussed in the reviews
by Dehmer et al. [4.67] and Nenner and Beswick [4.101].
Figure 4.7 shows that the energy position of the 0'* resonance is very
sensitive to the internuclear distance, a fact which has been discussed extensively
[4.79,92,94, 102, 103]; see Fig. 4.5. Systematic inspection of the 0'* resonance
position for different bonds reveals that it is a function not just of the bond
length but also of the detailed molecular potential. This dependence can be
approximated by consideration of the atomic numbers Z of the bonded atoms
[4.79]. For most low-Z molecules the 0'* resonance lies in the continuum above
the IP, but if the sum of atomic numbers of the two bonded atoms exceeds
Z = 15, it falls below the IP such as in O 2 [4.79, 104]. Measurement of ion
angular distributions is an elegant way to obtain final state symmetry informa-
tion [4.105] and this technique has recently been used to confirm the assignment
of the position of the 0'* resonance in O 2 [4.106]. The important correlation
between the 0'* resonance position and bond length is discussed in detail in
Chap. 8. The intensity of the 0'* resonance for a given bond length increases with
Z, being weakest for C-C bonds and strongest for F-F bonds.

4.2.5 Multi-Electron Features

Multi-electron effects have already been discussed in Sect. 2.5, and we saw that,
in principle, all electronic excitations are multi-electron in nature. The reason for
using a one-electron model, at all, stems from its simplicity and success in
explaining photoemission spectra that are dominated by peaks originating from
the "active" electron. However, closer inspection of photoemission as well as
absorption spectra reveal satellite peaks which can be associated with the
indirect excitation of "passive" electrons. The sudden creation of the core hole
potential induced by the absorption of an X-ray photon by the "active" electron
may knock one or more of the "passive" electrons into excited states.
In a simple picture, two types of effects can be distinguished. When the
excited state is a bound state, the process is called a shake-up, and when it is a
continuum state the process is referred to as a shake-off. In both processes the
total excitation energy is equal to the photon energy and in photoemission
spectra the satellites are therefore observed at lower kinetic energy than the
main active-electron peak. In X-ray absorption or ISEELS, multi-electron
features related to a specific primary transition are observed at higher photon
energy than the primary resonance. In general, shake-up structures are peak-like
while shake-off structures are step-like or just a smooth background.
Probably the best known multi-electron effects in K -shell spectra are those
in argon, first observed in 1963 [4.107] and extensively studied ever since by
96 4. Experimental and Calculated K-Shell Spectra of Simple Free Molecules

Fig. 4.8- K-shell X-ray absorption

Argon spectrum of argon near threshold
K-edge (compare Fig. 2.1), recorded by
4 Lytle et al. [4.111]. The energy re-
(jj" gion containing various shake-up
.~
c: structures is shown enlarged under-
::l
neath and is plotted on an energy
-e 3 scale relative to the IP. Most of the
~ satellite peaks can be attributed to
1:)
m
;;::
two-electron excitations of Is and
3p electrons [4.109]
c: 2
e
uQ)

iii

3200 3220 3240 3260

Photon Energy (eV)

means of X-ray absorption [4.108, 109] and photoemission [4.110], spectro-

scopies. The Ar K-shell spectrum recorded by Lytle [4.111] is shown in Fig. 4.8
and exhibits large multielectron structures in the range 15-50eV above thres-
hold. Similar structures are also observed in the K-shell spectrum of neon
[4.112]. These shake-up structures arise from two-electron transitions involving
the 1s and 3p electrons with binding energies of [Link] and 15.8 eV, respect-
ively. As expected, the satellites are separated from the 1s IP by more than the 3p
binding energy because of the additional Coulomb and exchange terms associ-
ated with the two-hole final state [4.113] and correlation effects. In fact, the
main satellite peak is separated from the 1s IP by approximately the 3p binding
energy (18.3 eV) of the equivalent core atom, potassium. The various shake-up
peaks are associated with different electronic final state configurations, of which
the 1s3p 53d2 and 1s3p54p2 configurations give rise to the largest transition
strengths [4.109]. It has been pointed out that, in particular, the main two-
electron resonance at 3225 eV is associated with the 1s3p 53d 2 configuration and
that it can be reached via 1s-3p double excitation from a correlated ground state,
consisting of the pure 1S23p6 ground state mixed with double-excited 1S23p4
nln'l configurations.
Examples of shake-up structures in molecular K -shell spectra can be found in
the N 2 K -shell spectrum (Fig. 4.3), and the C K -shell spectrum of CO (Fig. 4.5).
In both cases a pronounced peak-like structure exists about 5 eV above the IP,
just below the u* shape resonance. High resolution spectra (Fig. 7.1) reveal
considerable fine structure in this resonance [4.21,54, 114], owing to its origin
as a double excitation feature. For example, in CO the double excitation
involves the final state configurations (1s) -1 (br) - 1(2n*)1 (Ryd.)1 and
(1s) -1 (5u) -1 (2n*)1 (Ryd.)1 resulting from transitions of the "active" 1s electron
 4.2 Characteristic Resonances in K-Shell Spectra 97

and a In or 5u "passive" valence electron to the 2n* and Rydberg orbitals,

respectively [4.21, 60-63, 87]. Careful inspection of the 0 K-edge spectra of CO
and H 2 CO in Fig. 4.5 reveals other weak structures in the continuum above the
u* shape resonances which also appear to be multi-electron in character.
Multielectron excitations involving double-core-vacancy excited states have
also been observed in molecular gas phase spectra [4.113, 115] and solids
[4.116]. Such features may lie several hundred eV above the IP and therefore
interfere with the EXAFS structure. Shake-up peaks can also be observed in the
near edge spectra of solids, as discussed by Stern [4.117].
To develop a better understanding of the origin of various resonances we
present below a comparison of selected experimental and theoretical results for
K-shell excitation spectra of simple molecules.

4.2.6 Correlation of Multiple Scattering and Molecular Orbital Calculations:

The N 2 Molecule
The N 2 molecule has served a special role over the years. It was not only the first
test case for the quantitative calculation of molecular K-shell spectra (for a
review see [4.67]) but it has also been thoroughly explored experimentally and
theoretically, deepening our understanding of the various phenomena associ-
ated with photoionization [4.67,91]. As a consequence, its K-shell spectrum has
been thoroughly studied experimentally [4.8, 16, 17,21,54, 71, 113, 118] and
theoretically [4.59, 60, 88, 95, 97, 100, 119-121] and provides a suitable example
as to the present extent and limitations of our understanding.
The experimental X-ray absorption cross section for N2 measured by
Bianconi et al. [4.118] is compared in Fig. 4.9 to the results calculated by Dehmer
and Dill with the Xoc-MS method [4.88] and by Rescigno and Langhoffwith the
MO St'ieltjes-Tchebycheff [4.95] technique. The MS and MO calculations give!
numbers for the n* resonance of 0.23 and 0.26, respectively. Since the total
(discrete and continuum) oscillator strength for the K-shell of the low-Z atoms is
approximately equal to 2, (2.15), the number of K-shell electrons [4.122], the n*
resonance intensity is about 10-15% of the total K-shell absorption intensity.
The corresponding n* resonance cross sections shown in Fig. 4.9, obtained by
means of (2.14) with a peak width l/(lb = 1 eV, are in good agreement with
experiment. The energy position of the n* resonance is 4 eV lower than experi-
ment for the MO calculation and 2eV higher than the measured value for the
MS theory.
The continuum cross sections obtained with the two techniques differ in
magnitude and the u* resonance position. The MO theory yields the continuum
cross section in excellent agreement with theory and the u* resonance is within
5% of the experimental intensity. The MS calculation overestimates the u*
resonance intensity by a factor of 1.6. At first sight it therefore appears that the
MO-ST calculation is superior to the Xoc-MS calculation in reproducing the
absolute transition intensity. However, we need to remember that both calcu-
lations are one-electron calculations and completely ignore multi-electron
98 4. Experimental and Calculated K-Shell Spectra of Simple Free Molecules

Photon Energy hv (eV) Fig.4.9. (a) X-ray absorption cross section

400 410 420 430 440 450 for N2 measured by Bianconi et al. [4.118].
4 Superimposed on the spectrum as a dash-
A
N2 Experiment (a) dotted step function is twice the calculated
atomic N cross section [4.88]. (b) Calculated
3 xO.2 N2 K-shell excitation spectra by means
B of X<x-MS theory [4.59, 88] and
2 Stieltjes-Tchebycheff MO theory [4.95]. Note
that, although the calculated energy positions
for the n* and (1* resonances are about 3 eV
off the measured positions, the n*--O'* splitting
:c is reproduced within 1 eV by both calcu-
~
)( 0 lations. Also shown is the atomic step function
b
~A
of (a)
c: N2 Theory (b)
.2 5
""
UQ) """
en ""
rn
rn 4 " xO.2 B
0
0
3

2
""
rJ'-I
I
I
I
I '

-.-2 ___
""
"
o ""
-10 o 10 20 30 40
hv - IP (eV)

effects. Because such effects lower resonance intensities, one-electron calcu-

lations should overestimate the continuum resonance intensities, as discussed in
Sect. 2.5. In addition, continuum resonances are expected to be broadened by
vibrational effects as illustrated in Fig. 4.7. With respect to the 0'* position, both
calculations are off by 3 eV; the MO calculation places the resonance too low in
energy, while the MS calculation places it too high by the same amount.
Although the absolute 1t* and 0'* energy positions are incorrect by 2-4 eV, the
n*-O'* splitting is accurately predicted within 1 eV by both calculations.
The dependence of the 0'* resonance position and intensity for N 2 on the
molecular potential, calculated by means of the X/X-MS method, is shown in
Fig. 4.10. As our reference spectrum, we have recalculated the original results by
Dehmer and Dill [4.88], shown in Fig. 4.9. Our results for the continuum cross
section and potential are shown as solid lines in Fig.4.10d and Fig.4.10a,
respectively. The potential was constructed self-consistently with muffin-tin
radii of 0.55 A around the atomic centers, and an outer sphere radius around the
molecular center of 1.10 A, and is identical to that previously shown in Fig. 2.7.
The potentials are plotted along the internuclear axis as a function of the
distance Irl from the center of the molecule. Our reference potential and the
 4.2 Characteristic Resonances in K-Shell Spectra 99

Xa-MS Potentials and Cross Sections for N2

O~~-r __ ~~-r--~~~--r-~

leI "
-20 _ -20
>
~
-40 j:: -40
>
-60 ~c: -60
.,
o
;; -80 <>.
-80 Core
~ Hole
E
>
-100
-2 -1 o 2
~c: Distance from Molecular Center (AI Distance from Molecular Center (AI
0
5
<>. Ibl , ,-
Idl - - - - Touching spheres
/ 1\ tranSition state
-20 \ I
1 II _ . - OverlapPing spheres
II tranSition state
II
-40 II - - - Touchmg spheres
II self-consistent
I I T~uchlng spheres
I I
-60 I \ Non-self-conSistent
I \
I \
I \ r" '-..
-/
I\./
=.........._-...j
/ ' -...~-':.:~'---=-,",.

425 430 435

Distance from Molecular Center (AI Excitation Energy (eV)

Fig. 4.10.-4. Molecular potentials for N2 as a function of the distance Irl from the center of the
molecule, calculated by the Xcx-MS technique and the corresponding continuum cross sections. As a
reference we have chosen the self-consistent touching-sphere potential of Fig. 2.7, which was also
used by Dehmer and Dill [4.88] for their cross section calculation shown in Fig. 4.9. This potential
and the corresponding continuum cross section are shown as solid lines. Note that we have omitted a
vertical line in the solid-line potential at the molecular center (Fig. 2.7), which would indicate the
value ofthe "inner potential", in order to more clearly show it in the other potentials, calculated with
different assumptions. (a) Comparison with a potential (dotted line) calculated non-self-consistently
with the same sphere radii as the solid-line potential, by simple superposition of the atomic XIX
charge densities for nitrogen atoms. (b) Comparison with a potential (dashed line) calculated self-
consistently with the same parameters but using the transition state approximation where half an
electron was removed from the Is shell of one of the nitrogen atoms. (c) Comparison with a potential
(dashed-dotted line) calculated for atomic spheres of radius 0.63 A (overlapping spheres) and an outer
sphere of radius 1.18 A, using the transition state approximation. In this case the sphere radii were
determined by demanding that the calculated ls IP agreed with the experimental value of [Link].
(d) Comparison of the continuum cross section calculated with the potentials in (a-c). The line
patterns of the curves correspond to the ones chosen for the potentials

corresponding continuum cross section are compared to three potentials and

cross sections calculated with different assumptions. The potential shown as a
dotted line in Fig. 4.10a and the corresponding cross section in Fig. 4.l0d were
calculated non-self-consistently with the same sphere radii (touching spheres) as
the solid-line reference potential by simple superposition of the atomic Xa
charge densities for nitrogen atoms. The potential shown as a dashed line in
Fig. 4. lOb and the corresponding cross section were calculated self-consistently
tOO 4. Experimental and Calculated K-Shell Spectra of Simple Free Molecules

with the same parameters but using the transition state approximation where
half an electron is removed from the Is shell of one of the nitrogen atoms.
Finally, the dashed-dotted potential in Fig.4.10c and the dash-dotted cross
section were calculated for atomic spheres ofradius 0.63 A (overlapping spheres)
and an outer sphere of radius 1.18 A, using the transition state approximation.
In this case the sphere radii were determined by setting the calculated Is IP to
the experimental value of [Link].
Ofthe various potentials shown in Fig. 4.10, the overlapping-spheres trans-
ition state calculation (dash-dotted) yields the a* resonance position (418.5 eV)
in best agreement with the experimental value of 41geV. As discussed by Wurth
and Stohr [4.64], the success of this approach is based on the semi-empirical
choice of the sphere radii to fit the experimental ionization potential. The a*
positions for the other potentials fall at 413.5 eV (dashed), 421.5 eV (solid), and
424eV (dotted), with the results for the touching-spheres transition state (dashed
line) showing the largest discrepancy with experiment.
The theoretical XIX-MS and MO-ST methods discussed in Chap. 2 provide
us with a complementary view as to the origin of the observed K-shell reson-
ances. For example, it is easy to understand in the MS picture why a correlation
exists between the a* resonance position and the bond length. In a scattering
picture the excited photoelectron gets trapped by the molecular potential in
the direction along the internuclear axis. It scatters back and forth between the
absorbing atom and its neighbor and in a simple EXAFS-like picture the
resonance condition is expected to depend on the inter-nuclear distance Rand
the photoelectron wavevector k, according to Rk = const., or Ek = const./R 2 ,
where Ek is the kinetic energy of the photoelectron, i.e., the energy above
threshold in the K-shell spectrum [4.92]. On the other hand, the MO picture is
very helpful for visualizing the origin of the resonances in terms of molecular
orbital pictures of the final states, as plotted for example, by Jorgensen and
Salem [4.58]. The question arises as to a link between the two seemingly
different MS and MO approaches. Such a link can indeed be established, and we
shall discuss it here for N 2 • In particular, we shall focus on the calculations for
the continuum a* shape resonance which is more intriguing than the n* bound-
state resonance. As mentioned above, calculations for bound states can be
carried out with great accuracy by MO theory (for N2 see [4.121]), while it is
more difficult to obtain reliable results for continuum states.
The MS picture views the a* shape resonance as a final ionic state in which
the photoelectron is trapped by the molecular potential in the direction of the
internuclear axis [4.59, 88]. The large oscillator strength of the transition arises
from the large spatial overlap of the core initial state with the compact final
state, trapped in the inner potential well (Fig. 4.2). The effective potential barrier
that limits the motion of the excited photoelectron is a centrifugal barrier [ oc I
(I + 1)/r2] for the 1 = 3 orfwave component of the au ionization channel. This
can be understood as follows. In an atomic picture (region I in Fig. 2.6) the
dipole excitation of a Is initial state leads to a p-like (l = 1) final state which
upon escaping to infinity is scattered by the anisotropic molecular potential into
 4.2 Characteristic Resonances in K-Shell Spectra 101

the entire range of angular momentum states contributing to the a ionization

channel. When the au wavefunction is expanded about the center of the molecule
(coordinate r in Fig. 2.6) it is the 1= 3 component which is resonantly trapped at
a particular kinetic energy of the photoelectron.
A seemingly different explanation for the a* resonance arises from MO
calculations. As first discussed by Rescigno and Langhoff [4.95], and later

(a) N2 3a~ Antibonding Orbital

(b) N2 Resonant au 2 =3 E igenchannel Wavefu net ion

2
'Ita
o
-2

-1
o

(e) N2 au 2=3 Wavefunction on and off Resonance

12.2 eV

16.3 eV

20.4 eV

Fig. 4.11. (8) Picture of the 317: anti bonding molecular orbital in N2 taken from [4.58], which in a
molecular orbital picture is the final state of the u· resonance excitation. (b) Eigenchannel contour
plot of the resonant 1= 3 uu Xa-MS wavefunction taken from [4.120]. The N2 molecule lies along
the z-axis with its center at y = z = O. Note the close correspondence of the central contours in the
y-z plane with the shape of the orbital in (a). (c) Radial plot from the molecular center of the I = 3 uu
Xa-MS wavefunction at different final state energies, below (12.2 eV), at (16.3 eV), and above 20.4eV)
resonance. The nuclear position of N is also marked. Note that the shape resonance wavefunction is
strongly localized on the molecule
102 4. Experimental and Calculated K-Shell Spectra of Simple Free Molecules

clarified by Hermann and Langhoff[4.96] and Thiel [4.97], the (1* resonance can
be understood in a MO picture as arising from a transition to the 3(1~
unoccupied virtual orbital. This orbital, plotted in Fig. 4.11a, is spatially com-
pact, giving rise to the large (1* resonance intensity, and has p-like lobes along
the internuclear axis, centered on each N atom.
The link between the MS and MO concepts is established most elegantly by
viewing the MS wavefunction (Sect. 2.7.4) as similar to the contour maps used
for picturing MOs. This is done in Fig. 4.11, where the orbital contour of the 3(1~
molecular orbital is compared with the resonant I = 3 eigenchannel wave-
function for N2 [4.120]. In Fig. 4.11b, the N2 molecule lies along the z-axis with
the center of the molecule at y = z = O. At large distances the wavefunction has
the three nodal planes characteristic off orbitals. However, the four innermost
"orbital" contours, best visualized as the projection in the y-z plane, show a
striking resemblance with those of the 3(1~ molecular orbital in Fig. 4.11a. The
local p-like symmetry of the final state MS wavefunction at the site of each of the
two N atoms can again clearly be seen in the y-z plane projection. The
enormous enhancement of the wavefunction at resonance (16.3 eV) and its
compact spatial extent, with an intensity peaking at the N atom position, is
shown in Fig. 4.11c. Note that the (1* resonance energy in Fig. 4.11c is higher
than that in Fig. 4.9 because a different rx value was used in the exchange
potential (2.56).
The close correspondence between MS shape resonances and transitions to
antibonding molecular orbitals demonstrated for N2 holds quite generally and
in the following we shall discuss this useful correlation for a particularly
important class of molecules, the hydrocarbons.

4.2.7 Molecular Orbitals and Resonances of Simple Hydrocarbons

Because of their importance in catalytic processes and as the backbone of
polymers, hydrocarbons warrant special attention. The basic building blocks of
such systems are C-C bonds of different hybridization and additional C-H
bonds and we therefore expect their K-shell spectra to exhibit all the various
features discussed in the preceding sections.
Experimental ISEELS spectra for the simple hydrocarbons acetylene
(HC=CH), ethylene (H 2C=CH 2), and ethane (H 3 C-CH 3 ), shown (Fig. 4.12a)
exhibit rather complex structures. In particular, for C 2H 2 and C 2H 4 there are
many resonances above the IP, and at first sight it is difficult to make an
unambiguous assignment of the (1* shape resonances. It is for this reason that
the assignment of Sette et al. [4.79, 103], which was based on systematics of (1*
resonance positions in a variety of molecules was criticized by Piancastelli et al.
[4.123, 124].
Compared to the experimental spectra, the spectra calculated by means of
Xrx-MS theory [4.64] shown in Fig.4.12b are much simpler and exhibit the
various resonances expected from our previous discussions of other molecular
K-shell spectra. In particular, the Xrx-MS calculation for C 2 H 2 is in good accord
 4.2 Characteristic Resonances in K-Shell Spectra 103

Experiment Theory

rr* (a) rr* (bl

0*
0*
x5

x3

280 290 300 310 320 280 290 300 310 320
Excitation Energy (eV)

Fig. 4.12. Comparison of experimental ISEELS K-shell excitation spectra of acetylene (HC=CHl
[4.51], ethylene (H 2 C=CH 2 l [4.27], and ethane (H3C-CH3l [4.81] with XIX-MS calculations of the
same molecules [4.64]. Comparison of experimental and theoretical spectra indicates that all
resonances shown shaded originate from multi-electron transitions

with that carried out using the MO-ST method [4.125]. The good agreement of
experiment and theory shown in Figs. 4.4 and 4.5 indicates that many of the
peaks above the IP in the C 2 H 2 and C 2 H 4 spectra are of multi-electron
character, which the calculation, of course, does not reproduce. We have shaded
those structures in Fig. 4.l2a. In particular, in agreement with our classification,
the prominent peaks at 295eV in the C 2 H 2 spectrum and at 293eV for
C 2 H 4 have been attributed to two-electron excitations of the kind
(1s}-1(1n) - 1(2n*)1(RydV [4.63, 126, 127]. The involvement of the n system in
the double excitation process is also indicated by the absence of such resonances
in the spectrum of C 2 H 6 , shown at the bottom of Fig. 4.12.
Because the spectra of unsaturated hydrocarbons contain discrete n*, C- H*
and Rydberg features, it is interesting to compare the density of the associated
orbitals. This is done in Fig. 4.13 for the ethylene molecule. Again the Xcx-MS
method was used [4.64] and the core hole was located in the upper C atom,
indicated C*, in Fig. 4.13a. The labeling corresponds to the C 2v symmetry of the
excited molecule. The orbital contours show that the 2b 1 orbital, associated with
the n:.* resonance in the spectra in Fig. 4.12, is the most compact, in agreement
with the large resonance intensity. In comparison, the density of the 3b 2 C-H*
orbital and the 3b 1 Rydberg orbital which both contribute to the peak near
288 eV in the C 2 H 4 spectra in Fig. 4.12 is smaller by about a factor of 5. Note
that the C-H* orbital clearly exhibits density at the positions of the H atoms.
This orbital corresponds to the 2b 3u MO (D 2h symmetry) plotted by Jorgensen
104 4. Experimental and Calculated K-Shell Spectra of Simple Free Molecules

(a) Geometry (b) 3b 2 Orbital (e-H')

x5
H

H H
y-z plane

(e) 2b 1 Orbital (71') (d) 3b 1 Orbital (Rydberg)

~ . .

• x-z plane
J x-z plane
l
Fig. 4.13a- d. Geometry and orbital contour plots of several obitals for ethylene. The irreducible
presentations correspond to the C 2Y broken symmetry in the presence of a core hole, placed on the
upper C atom labeled C*. The 3b 2 orbital shown in (b) is ofC-H* valence nature and gives rise to the
resonance at 288eV in the C 2 H4 spectra in Fig. 4.12. The 2b , orbital is the n* orbital associated with
the C = C bond and with the n* resonance near 285 eV. The 3b l orbital is of pure Rydberg nature
and, like the 2b , orbital, it is perpendicular to the molecular plane containing the hydrogens. It also
contributes to the resonance at 288 eV in Fig. 4.12. Note the reduced density of the C-H* and
Rydberg orbitals relative to the n* orbital, yet the similar density of the Rydberg orbital and the
C-H* valence orbital

and Salem [4.58]. The similar density ofthe 3b 1 Rydberg orbital is in contrast to
the conventional picture of a diffuse nature of Rydberg orbitals. Our results
therefore underscore the fact known from elementary quantum mechanics
[4.28] that this picture only holds for the higher members of the Rydberg series
while the first members, e.g., the 3b 1 orbital, are rather compact.

4.2.8 Exchange Splitting in the Oxygen Molecule

The open shell oxygen molecule is expected to exhibit a magnetic exchange
splitting of the (1* resonance. Such a splitting is indeed observed. In accordance
with the simple MO diagram shown in Fig. 3.1 Ie, the spectrum calculated by
means of a self-consistent spin-dependent XIX-MS calculation and the gas phase
ISEELS [4.51] spectrum exhibit three peaks, as shown in Fig. 4.14. The calcu-
lation utilized Slater's transition state method and a semiempirical choice of the
muffin-tin spheres, i.e., adjustment of their radii to yield the spin-dependent
experimental Is ionization potentials [4.128] 543.1 eV (41' ionic final state) and
544.2 eVe l' ionic final state) for the O 2 molecule.
 4.2 Characteristic Resonances in K-Shell Spectra 105

Fig. 4.14. (a) Spin- and polarization-

(a) Theory resolved NEXAFS spectrum calculated
-----" 9
.. " ¢ by means of self-consistent XCl multiple
scattering theory. All calculated oscil-
--u9 lator strengths were converted into
---u9 cross sections by convolution with a
Gaussian of [Link] FWHM. The calcu-
lated ionization potentials (same as
measured) corresponding to 4}; and 2 J;
ionic final states are also indicated. (b)
Experimental electron energy loss
spectrum of gas phase O 2 [4.51]
(b) Experiment

530 532 534 536 538 540 542 544 546

Excitation Energy (eV)

The labeling of the resonances in Fig. 4.14 is chosen to agree with that used
earlier for Fig. 3.11c. Resonance A at ~ 531 eV corresponds to the lau -+ In:
transition. According to Hund's rule, in the ground state, the two degenerate
n:
1 orbitals of O 2 are each singly occupied by electrons with parallel spins, and
we shall assume that their spins are up, as shown in Fig. 3.11c. The Pauli
principle and the dipole selection rule which forbids any spin-flip transition then
demand that the 1i* resonance corresponds to excitation of a spin-down electron
from the Is shell (lau orbital).
Resonances Band C in Fig. 4.14b primarily correspond to a* resonances,
i.e., spin-up and spin-down lag -+ 3a: transitions, respectively, the splitting
arising from two different final state spin configurations, see Fig. 3.11c. The
exchange splitting of the a* resonance in the gas phase spectrum in Fig. 4.14b is
remarkably large ( ~ 2.5 e V), and exceeds the calculated splitting (1.2 eV) in the
a* system shown in Fig. 4.l4a. This quantitative difference is due to the limited
accuracy of the calculated transition energies 3 but it does not affect the qualitat-
ive reliability of the calculated spectra.

3 In the XCl-MS transition state calculation we removed one half electron from the Is shell. This
allowed us to calculate the whole spectrum with the same potential. In order to calculate transition
energies between two orbitals more accurately one should also add half an electron to the upper
orbital. In our case this procedure would have resulted in an "orbital energy" for the 3u! orbital
above the vacuum level and was therefore not used.
106 4. Experimental and Calculated K-Shell Spectra of Simple Free Molecules

Closer inspection of all transitions calculated by the Xo:-MS method reveals

that the schematic molecular orbital picture given in Fig. 3.l1c is oversimplified
in that it neglects the influence of Rydberg orbitals. The calculation predicts
several transitions to Rydberg orbitals of n character which mostly fall in the
region of resonance C. These transitions are also shown in Fig. 4.14a and have
been broadened by the same 1.0eV Gaussian function as all other calculated
transitions. Furthermore, resonance C itself is composed of two roughly equal
components of spin-down character which are not resolved in Fig. 4.14. We
believe this splitting to arise from a mixing of Rydberg orbitals with the 3a!
valence orbital. For O 2 the 3a! valence component dominates, as discussed
earlier in Sect. 4.2.3 in conjunction with Rydberg and hydrogen-derived reson-
ances. This valence-like nature of resonances Band C has the important
consequence that they are expected to remain largely unaffected by extra-
molecular bonds, in contrast to pure Rydberg resonances. As shown in Chap. 10,
this is supported by results for solid O 2 and physisorbed O 2 ,

4.3 Systematics of Resonance Positions

In our overview of the various characteristic resonances encountered in K-shell

spectra of low-Z molecules, we have already indicated a hierarchy of energy
positions. Typically n* resonances are lowest in energy, followed by Rydberg
and/or hydrogen-derived resonances and, at the highest excitation energies, a*
resonances. Here we are interested in the energetics of a characteristic resonance
within differently bonded molecules, e.g., the energy position of the n* resonance
in molecules with C=C, C=C, C=N, or C=O bonds. We shall restrict our
discussion here to "simple" molecules as defined in Sect. 4.2.1. This insures that
the resonances are characteristic of well-defined local bonds and not disturbed
by bond-bond interaction effects.
In our attempt to understand systematics among characteristic resonances,
it is advantageous to compare relative rather than absolute resonance positions.
If we ignore Rydberg transitions, a K-shell resonance corresponds to a trans-
ition from a localized Is to a molecular orbital final state which is delocalized
over the bonded pair of atoms. Therefore, transitions to the same MO can be
observed by Is excitation of either atom participating in the bond. For example,
the n resonance in CO is observed at the C as well as the 0 K-edge (Fig. 4.5). It is
to be expected that, although the absolute excitation energies for a characteristic
resonance are substantially different at different K-edges, the resonance posi-
tions relative to the respective Is IPs should be rather similar. This is because the
resonance position relative to the IP is a direct measure of the orbital energy of
the excited state MO (the "optical orbital") relative to the vacuum level, Ev , as
discussed in Sect. 2.6.1 and illustrated in Figs. 2.4, 4.2. By referencing resonance
positions to the corresponding IPs we can therefore significantly increase our
data base. Other reasons for this procedure will become apparent later.
 4.3 Systematics of Resonance Positions lO7

Table 4.1. n* resonance positions and Is ionization potentials in nonconjugated simple molecules

Is ionization n* resonance
potential' position ~. = E. - IP
z· Molecule b IP [eV] E.[eV] [eV] Reference

12 HC=CH 291.1 285.9 - 5.2 4.129

H 2 C=CH 2 290.8 284.7 - 6.1 4.27
F 2 C=CF 2 296.5 290.1 - 6.4 4.27
13 HC*=N 293.4 286.4 -7.0 4.130
HC=N* 406.8 399.7 - 7.1 4.130
14 N=N 409.9 401.0 - 8.9 4.54
C*=O 296.2 287.3 - 8.9 4.54
C=O* 542.5 534.1 - 8.4 4.54
H 2 C*=0 294.5 286.0 - 8.5 4.73
H 2 C=0* 539.4 530.8 - 8.6 4.73
F 2 C*=0 299.6 290.9 - 8.7 4.73
F 2 C=0* 540.8 532.7 - 8.1 4.73
15 N*=O 4lO.7 d 399.7 - 11.0 4.131
N=O* 543.2d 532.7 -lO.5 4.131
CF3N*=0 410.5 399.1 - 11.4 4.132
CF 3N=0* 542.3 530.8 -11.5 4.132
16 0=0 543.7 d 530.8 - 12.9 4.54

• Sum of atomic numbers of bonded pair

b The excited atom is indicated by an asterisk

, For a tabulation of IPs, see [4.55]

d Weighted average of doublet

Let us start with the lowest energy resonance observed for all unsaturated
bonds, the 11:* resonance. We have summarized in Table 4.1 the 11:* resonance
position E", the corresponding IP, and the difference ~" = E" - IP in a variety
of "simple" molecules. Note that -~" is usually called the term value in the
literature. We prefer our (opposite) sign definition of the energy difference
because it directly reflects whether the optical orbital lies below (negative
energy) or above (positive energy) E v , in accordance with the definition of
calculated orbital energies. We have grouped the molecules in Table 4.1 accord-
ing to Z, the sum of atomic numbers of the bonded atomic pair, such that a C-C
bond is characterized by Z = 12, etc. Within each group we have listed mole-
cules with different bond orders (triple and double bonds) and different 1s IPs,
arising either from excitation of different atoms or from chemical shifts for a
given atom [4.55].
Within each group, the 11: resonance position relative to the IP is remarkably
constant, to within about 1 eV, independent of the hybridization, the atom
whose K-shell is excited, and chemical shifts of the 1s IP. The independence of
~" to hybridization, and therefore bond length, can be understood by the
orthogonality of the 11: system to the internuclear axis and the resultant small
change in overlap of the p functions on adjacent bonded atoms as a function of
bond length. As expected from the delocalized nature of the MO final state, the
108 4. Experimental and Calculated K-Shell Spectra of Simple Free Molecules

C K-edge Fig. 4.15. Carbon K-shell excitation spectra of

some fluorinated aldehydes [4.73]. In these mole-
15 cules the carbon Is IP exhibits a sizeable chemical
shift arising from charge transfer from carbon to
10 fluorine. When the spectra are plotted relative to
~
I the IP, it is seen that the Jr* and u* resonances
>Q) remain fixed in energy
C\I
I
5
0
10
.c 0
C,
c:
Q)
5
~
0 6
~ 4 o
·0
rn
0
2

-10 o 10
Energy from IP (eV)

energy ~" of the opticaln* orbital for heteroatomic bonds does not depend on
which atom gets excited. More surprizing is the insensitivity of ~" to chemical Is
binding energy shifts. This is illustrated in Fig. 4.15 for the carbon K-shell
excitation of fluorinated aldehydes, H 2C = 0, FHC = 0, and F 2C = 0, and in
Fig. 4.16 for the n* resonance in fluoroethylenes. For H 2C = CH 2, HFC = CFH,
and F 2C = CF2 (Fig. 4. 16a), the two carbon atoms in the molecule are equivalent
and the C Is IP shifts by as much as 5 eV upon fluorination, as for the aldehydes.
The n* resonance position follows this shift, leaving ~" unchanged. Further-
more, two distinctly shifted C = C n resonances are observed when the two
carbons are inequivalently bonded to hydrogen and fluorine as in H 2C = CHF,
H 2 C = CF 2, and HFC = CF 2 (Fig. 4.16b). The two n* resonances follow the IP's
for the respective carbon atoms.
Table 4.1 reveals that ~" is, however, dependent on Z, and the n* resonance
shifts away from the IP with increasing Z, corresponding to a lower-energy or
stronger-bound n* optical orbital. While the resonance is only about 5.5 eV
below the IP for C-C bonds, it is about 13 eV below the IP for the O 2 molecule.
This simply reflects the larger electron-nuclear Coulomb interaction, which
according to (2.19) increases with Z. To summarize, the n* resonance position
relative to the IP is mostly a function of Z, the sum of atomic numbers of the
bonded pair, and for a given Z is largely independent of hybridization, the
excited atom in a heteroatomic bond, and Is initial state chemical shifts. On an
absolute transition energy scale the n* resonance within a given Z group
therefore shifts with the Is IP.
The observations made for the n* resonances also hold for the Rydberg/C-H
resonances. The Rydberg/C-H resonances associated with the methyl group
 4.3 Systematics of Resonance Positions 109

10
10 8
,, ...... .C=C......... ,, 6
5 CH,
4

i 2
> 0
0
'1''" 295 8 H.... C..... ,
~ 10 = .... ,
H..... C
.r; 6
c;, ,H..... . .C=C.........H,
.."'" 5 4

..
Vi
0
2
:§ 0 0
'u., 8 5
0
6
H.... C C..... H
4
H..... = ....
H

Excitation Energy (eV)

Fig. 4.16a, b. K -shell excitation spectra near the 7[* resonances (shaded) for fluoroethylenes [4.27].
In (a) both carbon atoms are equivalent and their 7[* resonance position follows the IP, as for the
aldehydes shown in Fig. 4.15. For molecules with inequivalent carbon atoms, as in (b), two IPs and
two 7[* resonances are observed. Again, the 7[* positions move with the respective IPs

(CH 3-) are shown in Fig. 4.17 as a function of attached atoms or groups of
varying electronegativity. Similar to NH3 (discussed in Sect. 3.2.2), the CH 3
group is characterized by two empty Mas, a a*-like and a n*-like state [4.58].
Resonances A and B correspond to transitions to these final states which, as
discussed in Sect. 4.2.3, are mixed with Rydberg orbitals of the same symmetry.
The more intense n*-like resonance B occurs at 288.0eV in methane (CH3-H)
[4.53], [Link] in ethane (CH 3-CH 3) [4.81, 129], 288.5eV in methylamine
(CH 3-NH 2 ) [4.53], 289.4eV in methanol (CH 3-OH) [4.37, 53], and 290.5eV in
fluoromethane (CH3-F) [4.47, 51]. Its energy shift and that of the weaker
resonance A closely follows the chemical shift of the C Is IPs listed in the figure,
caused by the electronegative oxygen or fluorine ligands [4.55]. Thus, as for the
n* resonance of a specific atomic pair characterized by Z, the positions of the
Rydberg/C-H resonances are fixed relative to the IP.
In contrast to the rather simple behavior of the n* and Rydberg/C-H
resonance positions, the a* resonances exhibit a more complex energy depend-
ence. The representative data for molecules with "isolated", well-defined bonds
are summarized in Table 4.2, and their separation from the IP, .1a , is plotted in
Fig. 4.18 as a function of Z. In comparison we also show in this figure the data
110 4. Experimental and Calculated K-Shell Spectra of Simple Free Molecules

Fig. 4.17. ISEELS spectra of molecules containing

B
the CH 3 group and ligands with different electro-
negativities. Peak positions A and B marked by
solid lines correspond to RydbergjC-H resonances
and follow the listed C I s IPs marked by a dashed
line [4.55]. The shown spectra are taken from the
following references: methane [4.53], ethane
[4.81], monomethylamine [4.53], methanol [4.37],
and ftuoromethane [4.51]. The shaded resonances
are associated with transitions to (top to bottom)
C-C, C-N, C- O and C-F anti bonding (1* orbitals
(shape resonances). Note that for CH3F the C-F (1*
resonance by chance falls at the same energy as the
lowest RydbergjC- H resonance A [4.133]

290 300
Electron Energy Loss (eVj

15

c:
:2
·iii
o
Q.
Q)
()
c:
'"
g -5
"'
Q)
Fig. 4.18. Energy positions of n* and (1*
a: resonances relative to the K -shell IPs as a
-10 function of Z, the sum of atomic numbers
rr* of bonded atomic pairs (see Tables 4.1 and
4.2). Note the large scatter of data points
-15 for the (1* relative to the n* positions
which is caused by the strong dependence
12 13 14 15 16 17 18
of the (1* position on hybridization and
Sum of Atomic Numbers Z
bond length
 4.3 Systematics of Resonance Positions 111

Table 4.2. (1* resonance positions and Is ionization potentials in nonconjugated simple molecules

Is ionization (1* resonance ~a = Bond

potential e position Ea - IP length d
z· Molecule b IP [eV] Ea [eV] [eV] Ref. [A]

12 HC;=CH 291.1 310 19 4.129 1.203(1)

H 2C=CH 2 290.8 301 10 4.129 1.337(2)
H 3C-CH 3 290.7 291.2 0.5 4.129 1.533(2)
13 HC*=N 293.4 307.9 14.5 4.130 1.158(3)
HC=N* 406.8 420.8 14.0 4.130
H3C*-NH2 291.6 291.5 - 0.1 4.53 1.465(2)
H3C-N*H2 405.1 404.6 - 0.5 4.53
F3C-N*0 410.5 407.5 - 3.0 4.132 1.546(8)
14 N=N 409.9 418.9 9.0 4.54 1.095(5)
C*=O 296.2 304.0 7.8 4.54 1.128(5)
C=O* 542.5 550.0 7.5 4.54
H 2C*=0 294.5 300.5 6.0 4.73 1.209(3)
H2C=0* 539.4 544.0 4.6 4.73
B*-F3 202.8 205.1 2.3 4.134 1.313(1)
B-F! 694.8 699.0 4.2 4.135
H3C*-OH 292.3 292.0 -0.3 4.53 1.425(2)
H 3C-O*H 538.9 537.4 - 1.5 4.53
H2N-NH2 406.1 405.1 - 1.0 4.132 1.449(4)
15 N*=O 410.7" 414.5 3.8 4.131 1.150(5)
N=O* 543.2" 546.3 3.1 4.131
F 3CN*=0 410.5 413.2 2.7 4.132 1.197(5)
H3C*-F 293.5 289.1 - 4.4 4.5,47 1.382(5)
H3C-F* 692.4 691.0 - 1.4 4.136
16 0=0 54P" 540.5 - 3.2 [4.54, 104] 1.207(5)
N*-F 3 414.4 407.1 -7.3 4.137 1.365(2)
N-F! 693.2 687.4 - 5.8 4.137
HO-OH 541.8 533.0 - 8.8 4.138 1.475(4)
17 F 2-O* 545.3 534.6 -10.7 4.139 1.405(1)
F1-0 695.1 683.8 - 11.3 4.139
18 F-F 696.7 682.2 -14.5 4.140 1.417(5)

• Sum of atomic numbers of bonded pair

b The excited atom is indicated by an asterisk

e For a tabulation ofIPs, see [4.55]

d For a tabulation of bond lengths, see [4.70, 141]

• Weighted average of doublet

from Table 4.1 for ~'" the n* resonance positions relative to the IP. Compared
to the n* positions, the 0"* energies exhibit large scatter. At first sight, the only
obvious trend is that all data lie within upper and lower bounds shown as
dashed lines. The upper bound is determined by the molecules with the highest
bond order (triple and double bonds) for a given Z, and the lower by those with
the lowest bond order (single bonds). This is strong evidence that ~a, in addition
to Z, also depends on the bond length R, which, of course, changes with
hybridization. This dependence is also intuitively expected because the molecu-
112 4. Experimental and Calculated K-Shell Spectra of Simple Free Molecules

lar a orbitals lie along the internuclear axis, in contrast to the 11: system. We can
make the following two general observations: (1) /l." decreases with increasing Z,
similar to but stronger than /l.". (2) The spread in /l." decreases with increasing Z,
and the upper and lower bounds appear to converge near Z = 18 (the F 2
molecule).
Let us try to qualitatively understand the trends in /l." with Z as shown in
Fig. 4.18. This is best accomplished by first ignoring the complications intro-
duced by different bond hybridizations, i.e., bond lengths. Since the data points
appear to converge near F2 (Z = 18) let us take its bond length R =.1.417 A as
our reference. From Table 4.2 we see that the molecules F 2-0 (Z = 17) with
R = 1.405 A and H3C-OH (Z = 14) with R = 1.425 A have similar bond lengths
and their /l." values all lie approximately on the solid line marked
"R = 1.42 A" in Fig. 4.18. Hence to a good approximation this line represents
the Z-dependence of /l." at constant interatomic distance. Its slope is approxim-
ately a factor of 2 larger (3.5 eV for /l.Z = 1) th~m that ofthe corresponding line
for /l." (1.8eV for /l.Z = 1) also shown in the figure. The larger Z-dependence of
the a* relative to the 11:* resonance position can be understood from Fig. 3.1. As
discussed in Sect. 3.2, the 11: MOs originate from the 2px and 2py orbitals of
adjacent bonded atoms, and, while the energy of the two atomic p orbitals
decreases with Z, the 11:-11:* splitting is approximately constant. Therefore the Z-
dependence of the 11:* resonance follows that of the atomic p orbitals and is
dominated by the electron-nuclear Coulomb interaction. The a MOs originate
from the 2pz and the 2s atomic orbitals and therefore their energy positions
depend on both orbitals, in particular, their energy position and mixing. Owing
to the increasing energy separation of the 2p and 2s orbitals with increasing Z,
the 2pz-2s mixing is reduced substantially. From Fig. 3.3, we see that the 2pz-2s
splitting is about 10eV for carbon but about 25eV for fluorine. This greatly
affects the asymmetry of the positions of the outermost a and a* pair relative to
the atomic 2p level as shown for the 3ag and 3au states in Fig. 3.1. Hence with
increasing Z, not only is the energy position of the atomic 2p level lowered but
also the increasing separation from the 2s level, which drops considerably more
in energy with Z, causes the asymmetric a-a* splitting of the outermost pair to
diminish. The overall effect is a larger downwards energy shift of the highest a*
level than for the 11:* level.
The scatter of the data points around the solid R = 1.42 Aline in Fig. 4.18 is
caused by the strong dependence of the a* resonance position on hybridization
and bond length. Again it is easy to visualize the effect of a distance change
in a molecular orbital representation similar to Fig. 3.1. The a-(J* splitting is
strongly dependent on the internuclear distance because the overlap of the 2pz
orbitals on adjacent bonded atoms, which are directed along the internuclear
axis, changes greatly with distance. Hence, at short bond length the splitting is
larger than at longer bond length and the a* level is higher for small rather than
large R. Furthermore, with increasing Z the 11:* orbital becomes filled, being
empty at Z = 14 (N 2), half full at Z = 16 (0 2) and filled at Z = 18 (F2)'
Therefore the range of bond hybridization and bond length decreases with
 4.3 Systematics of Resonance Positions 113

increasing Z. While N 2 is triple bonded, O 2 is double and F 2 single bonded. The

attractive interaction caused by the filled 1t bonding orbital is compensated by
the repulsive interaction arising from filling of the anti bonding 1t orbital. This
leads to the convergence of the upper and lower bounds near Z = 18.
Because of its important applications in the study of chemisorbed molecules,
whose bond lengths are largely unknown, the detailed dependence of the u*
resonance position on bond length will be discussed in more detail in Chap. 8 for
free, polymeric and chemisorbed molecules.
5. Principles, Techniques, and Instrumentation
ofNEXAFS

In this chapter a basic question is addressed: How can the X-ray absorption
signal from a single molecular layer on the surface of a bulk material be
measured? In particular, electron yield and fluorescence yield detectors and
experimental techniques are discussed and specific attention is given to the
problems of normalization and background correction of experimental data.

5.1 Achieving Adsorbate Sensitivity

The link between K -shell spectra and intramolecular structure outlined in the
last chapter for free molecules points to the potential of near edge spectroscopy
for investigating the internal structure of chemisorbed molecules, as well. Here
we shall discuss how such spectra can be obtained experimentally. Compared to
gas phase spectroscopy there are two major complications associated with the
recording of spectra for molecules bonded to surfaces. First, the molecular
density on the surface is small. Typical surfaces have an atomic density of abou~
10 15 atoms/cm 2 and since molecules usually cover a surface in a single layer this
number also characterizes the molecular density. In contrast, for gas phase
studies the electron or X-ray beam traverses a volume of gas and the molecular
density can be adjusted at will. Typically it is chosen to be in the 10 17_10 18
atoms/cm 2 range. Secondly, the signal from the molecular layer is superimposed
upon an unwanted background signal from the bulk substrate. In particular, it is
the combination of the two problems, the low concentration of adsorbate atoms
and the high concentration of substrate atoms, which leads to experimental and
instrumental challenges.
For the study of chemisorbed molecules on surfaces the ISEELS technique is
not well suited. The use of high energy electron beams [5.1] in conjunction with
a transmission geometry through a thin film substrate 1, especially in the form of
single crystals, is undesirable because of the awkwardness and general unavail-
ability of such samples. Even if such substrates were readily available ex-
periments would be impeded by unfavorable signal-to-background ratios for
realistic thicknesses ('" 500 A) of free standing films. Radiation damage of the

1 High energy ISEELS measured in transmission through thin films is discussed in [5.2].
 5.1 Achieving Adsorbate Sensitivity 115

molecular adsorbate layer resulting from the high power density of the electron
beam [5.3] may also be a problem. For the same reason, reflection geometry
experiments [5.4, 5] are problematic, too, and they have only recently been
applied to the study of chemisorbed molecules [5.6, 7]. In addition, "polariza-
tion" dependent studies are difficult or impossible, which, as we shall see below,
make X-ray absorption studies so very powerful.
The above considerations indicate that for our purposes X-ray absorption
spectroscopy is indeed the technique of choice. NEXAFS studies, however, are
not without experimental and instrumental challenges. The small concentration
of surface species necessitates the use of high photon intensities, as demon-
strated by a quick estimate. Using the K-shell X-ray absorption cross section
1 Mb/molecule = 10- 18 cm 2/molecule for N2 from Fig. 4.9 and assuming a N2
monolayer of 10 15 molecules/cm 2 on the surface we find that it takes 103
photons to create one absorption event. Also, let us assume that we can monitor
each absorption event by collecting the photoelectron created in the event and
energy analyze and detect the electron with a total efficiency (solid angle,
transmission and detection) of 10- 3. Then, to obtain a count rate of 10 3
counts/s, needed for a spectrum with reasonable statistics, a photon flux of
1 x 10 9 photons/s is required. The low concentration of the molecules on the
surface therefore necessitates the use of powerful soft X-ray sources.
The additional requirement of high spectral resolution, which can only be
achieved in the soft X-ray region by monochromator optics with a small angular
acceptance [5.8-11], eliminates all but synchrotron radiation sources. Only for
highly collimated synchrotron radiation does the match of the emission charac-
teristics of the source and the small angular acceptance of the monochromator
provide for X-rays of sufficient intensity and energy resolution. In the following
we shall simply assume that monochromatic soft X-rays of sufficient intensity
are available. Although this statement is not rigorously true at the time of
writing it will certainly be true in the near future with the construction of new
powerful synchrotron radiation sources around the world.
The essence of the remaining problem is to find an experimental detection
method for the core excitation event which is specifically sensitive to the signal
from the molecule and insensitive to the background signal from the substrate.
For practicability we shall require that conventional substrates of macroscopic
dimensions (e.g., 10 x 10 x 2mm 3 ) can be used. This leads to a desired geometry
where the X-ray beam is incident on the surface of a sample at a specific but
variable angle and the characteristic signal from the adsorbate layer is measured
by use of a suitable detector which views the surface.
We want to measure a signal which is proportional to the X-ray absorption
cross-section crx(hv) defined by (2.8). In the limit of small adsorbate concentra-
tions, of interest here, the number of photons absorbed in the molecular layer is
(5.1)
where 10 [photons/(scm 2)] is the incident photon flux density, Ao [cm 2] is the
area exposed to the beam, which depends on the X-ray incidence angle,
116 5. Principles, Techniques, and Instrumentation of NEXAFS

Auger Fig. 5.1. Schematic diagram of a photon absorption

Electron process resulting in a photoelectron and a core hole.
Photo-
electron The hole is filled by an electron from a higher shell,
either radiatively by emission of a fluorescent photon,
or nonradiatively by emission of an Auger electron
-----+------+---Ev
----~--~~~-B

hv FI uorescent
Photon

----~--~-----A

p [atoms/cm 2 ] is the atomic area density and O"x(hv) is given in units of

Mb/atom = 10 - 18 cm 2 /atom. The number of absorbed photons is therefore
directly proportional to the X-ray absorption cross section and, according to
Fig. 5.1, so is the number of created core holes and photoelectrons. Figure 5.1
suggests that the most direct method of measuring the X-ray absorption cross
section of chemisorbed molecules is to monitor the intensity of the photo-
electrons which constitute the primary excitation channel. However, from
inspection of the energy scale of Fig. 4.2, it becomes clear that this is not a viable
method. All structures below the IP corresponding to bound state excitations
would be lost since only free photoelectrons are measured in photoemission.
This leads to the measurement of Auger electrons or fluorescent photons
associated with the secondary process of core hole annihilation. Both channels
are a direct measure of the probability of the existence of a core hole created by
X-ray absorption.
The secondary deexcitation process occurs either radiatively, by emission of
a fluorescent photon, or nonradiatively, by Auger electron emission. The
fractions of the nonradiative and radiative decay rates relative to the total decay
rate are called Auger yield Wa and fluorescence yield wJ' respectively, and satisfy
the sum rule Wa + wJ = 1 [5.12]. The relative yields are a strong function of
atomic number Z as shown for the K- and L-shell fluorescence yields of the
elements in Fig. 5.2a. For the K-shell excitation of low-Z atoms and for the L-
shell excitation of all atoms with Z < 90 the Auger decay is faster and hence
dominates [5.12]. In particular, for C, N, and 0 atoms the Auger electron yield
is favored over the fluorescence yield by more than two orders of magnitude, see
Fig. 5.2b. Nevertheless, as detailed below, both channels prove to be useful in
recording NEXAFS spectra of chemisorbed molecules.
Before discussing the principles and experimental techniques of electron
yield and fluorescence yield detection we should note the possibility of using a
third approach, namely ion yield detection, as a measure of the molecular cross
section. In the time evolution of events, molecular fragmentation and ion
desorption from the surface follow the primary excitation ( - 10- 18 s) and the
secondary Auger decay (_10- 15 s) as a tertiary (_10- 13 s) event. In a model
first suggested by Carlson [5.14] for free molecules and later by Knotek and
 5.1 Achieving Adsorbate Sensitivity 117

Fig. 5.2. (a) Overview of the fluorescence

yields following the excitation of K, L 3 , L 2 ,
and L, shells as a function of atomic number
Z [5.12, 13]. (b) Fluorescence yields for the K-
shell excitation of low Z atoms. We have used
0.20 the values listed in Table 3 of the review by
Krause [5.12]
0.10

0.05

0.02
"0
~
>-
'"uc
Atomic Number Z
'"~'"
u
(b)
0 10- 1 P~
Si

.--
.2
LL Mg AI

10-2
;./Ne Na

F=N
f-C
B'
10-3
o 500 1000 1500 2000 2500
Photon Energy (eV)

Feibelman [5.15] for ionic surfaces, the ion yield following core level excitation is
directly related to the Auger decay process. The repulsive forces between holes
created in the valence shell by an Auger decay may result in a "Coulomb
explosion" between two bonded atoms.
The question arises whether ion yield detection, in the form of individual
fragments or the sum of all ions, can be used as a measure of the X-ray
absorption cross section. Unfortunately, this is not the case for chemisorbed
molecules as first shown by Jaeger et al. [5.16] and displayed in Fig. 5.3 using
the data of Treichler et al. [5.17] for CO chemisorbed on Ru(001). The ion yield
spectra of various fragments are found to be significantly different from the
Auger electron yield spectrum shown at the bottom. The Auger yield with its
linear response to the core hole population mirrors the average of all decay
channels and is proportional to the X-ray absorption cross section. The detailed
Auger spectra of chemisorbed molecules furthermore reveal that the vast
majority of electronically excited states, in particular the multielectron ("shake-
up") states observed in photoemission, have boiled down to a well-screened
adiabatic state before Auger decay takes place [5.18-21]. In contrast, ion
fragmentation and desorption selectively follow the minority of cases where the
primary multielectron excitations survive long enough to influence fragmenta-
tion and desorption, aided by the additional holes created through Auger decay.
118 5. Principles, Techniques, and Instrumentation of NEXAFS

Fig. 5.3. Ion yields of CO +, 0 +, 0 2 +,

1«4<.~
..~' ' . ,. .
500
~ .~... ~,.~.<!("~~
.
and C+ following 0 K-shell excitation of
CO on Ru(OOI) in comparison with the
V~ co+ Auger electron yield spectrum obtained
100 .J by detecting 0 K VV electrons of 510 eV
kinetic energy [5.17]. Note that the ion
4000
~~~J'

__r
yield does not follow the Auger yield,
which is representative of the 0 K-shell
X-ray absorption cross section
« / 0+
E
0
0 1000
.......
~

en
.......
en
.....
C
::J
500 ~.r
2
0

100
./~'~~:'
"a; 200 :ti
>- ~Mt'-:.\.",~
100 '.AI":;'~ C+
en I J~
.'=
c
::J Vi\~
...
.ri
CtI J:I
o (KVV) Auger Yield
530540 550560 570 580590 600
Photon Energy (eV)

Therefore, the ion yield does not statistically average over all Auger decay
events. This explains the small desorption rates and steps in the ion yield spectra
in Fig. 5.3 that occur at energies associated with specific multielectron-
multi hole excitation thresholds. Ion desorption therefore demonstrates that in
order to measure the absorption cross section a detection technique has to be
used which statistically averages over all Auger or fluorescence channels.
In the following we shall discuss the principles and techniques of electron
and fluorescence yield detection.

5.2 Electron Yield Detection

5.2.1 Principles
The principles of electron yield detection require an understanding of the basic
photoemission events which follow the absorption of an X-ray by a solid. Note
that photoabsorption leading to emission of a photoelectron dominates by
orders of magnitude over all other interactions of soft X-rays (hv < 2 keY) with
matter such as coherent and incoherent scattering (Figs. 5.10, 11). A schematic
 5.2 Electron Yield Detection 119

EFl EV
Binding Energy (eV) 0 Kinetic Energy (eV)

-hv,-- - - - _ Photoemission

A B VB I (a)

(e)
Auger
/ VB
"'z:tz:=p,zt;J/1 :
Y1ield Window s:~~:~ I ' I

Total ~77777177m77==a0=3
Ep Ea

Fig.S.4a-c. Energy level diagram and schematic photoemission spectra at different photon energies
for a sample containing atoms with two core levels A and B and a valence band VB. The energy zero
is chosen at the Fermi level EF , which lies below the vacuum level Ey by the work function rjJ. (a) hv,
below the excitation threshold of core level A, (b) hV2 just above the absorption threshold of shell A
but below its photoemission threshold, (c) hV3 far above threshold of shell A. At each energy the
various photoemission and Auger peaks and their inelastic tails are indicated. At the bottom,
window settings for different electron yield detection modes are shown. In the Auger yield mode the
detector window is set around the energy Ea of the Auger peak. For partial yield detection only
electrons with a kinetic energy in access of Ep are detected while all electrons are collected in the total
electron yield mode

photoemission spectrum of a solid sample is shown in Fig. 5.4. We shall assume

that the sample consists of two kinds of atoms, adsorbate atoms which have a
core level A and a valence level which overlaps with the valence band (VB) of the
substrate, and substrate atoms with a shallow core level B and the VB. The
electron binding energies (Eb) are measured relative to the Fermi level (E F ) of
the substrate, as indicated. The Fermi level also defines the zero of the photo-
electron kinetic energy and is separated from the vacuum level (Ev) by the work
function cp.
As the photon energy is increased from below [hVl < Eb(A)] to just above
the absorption threshold [hV2 > Eb(A)] of shell A the creation of the core hole
results in the appearance of a characteristic Auger peak in the photoemission
120 5. Principles, Techniques, and Instrumentation of NEXAFS

spectrum at a kinetic energy Ea while the photoemission peaks move with the
photon energy. The Auger peak is characteristic of the adsorbate atoms and
originates from the decay of an adsorbate valence electron into the core hole in
shell A with transfer of the decay energy to another adsorbate valence electron.
At the shown energy hV2 the photoelectron excited from the adsorbate shell A is
not free to leave the sample because its kinetic energy is not high enough to
overcome the work function. As the photon energy is increased even more (hv3)
a photoemission peak corresponding to level A is observed while the Auger peak
remains at a fixed kinetic energy. The intensity of the Auger peak, however, will
change with photon energy and follow the X-ray absorption cross section of
shell A. Therefore, by use of an electron energy analyzer we can select a window
and center it at the fixed energy Ea of the Auger peak. The recorded intensity will
directly give the X-ray absorption cross section of the shell A of the adsorbate
atom.
The Auger electron yield (AEY) detection technique is illustrated for CO
adsorbed on Ni(lOO) in Fig. 5.5, taken from the early work of Stohr and Jaeger
[5.22]. Figure 5.5a shows the photoemission spectrum of the sample taken at a
photon energy of 550eV, about 15 eV above the 0 K-edge threshold. It directly

(a)
~ CO on Ni(100)
'c::l
Ni 3p hv=550eV
.c
~ 5.0
iU
c:
Ol
Ui OKVV
Ni VB
c: Auger
e
ti
Q)
2.5
c;;
o
(5
""a. ia

470 490 510

Electron Kinetic Energy (eV)

(b)

3 - - C O on Ni(100) Ni 3p
---Clean Ni (100)
>Q) I
0
U;
Ni VB
(40
w"
"0
c;;
2
I T .... Fig. 5.5. (a) Photoemission spectrum at hv
= 550eV for CO on Ni(I00) showing the 0
:;: KVV Auger peak of CO and the Ni 3p peak and
c: A B

ti
e J
valence band. (b) Auger electron yield NEX-
1 AFS spectrum recorded at grazing X-ray in-
Q)
iii
I
cidence for the CO covered and clean Ni(I00)
----- /
surface. The Auger yield was monitored by set-
ting the electron energy analyzer window at Ea
0
500 520 540 560 580 = 510eV as shown in (a). The spectra are taken
Photon Energy (eV) from [5.22]
 5.2 Electron Yield Detection 121

corresponds to Fig. 5.4b with the Ni 3p and VB representing the two substrate
levels B and VB, and the 0 Is level for level A. For Fig. 5.5b the window of the
cylindrical mirror electron energy analyzer (Fig. 5.7 below) was set around
510eV, the energy of the 0 KVV (K-shell valence-valence) Auger transition,
and its intensity was recorded as a function of photon energy near the 0 K-edge.
Figure 5.4 shows that the Ni 3p and VB photoemission peaks move with photon
energy and at a certain energy will therefore sweep through the detector
window, set at the fixed 0 KVV energy. This effect results in the two prominent
peaks at the lowest and highest energies in Fig. 5.5b. The two peaks in-between,
labelled "A" and "B", are characteristic of the 0 K-shell absorption. This is
proven by their disappearance for the clean Ni(IOO) surface. In fact, the two
peaks are the n* and 0'* resonances familiar from the 0 K -edge spectrum for free
CO shown in Fig. 4.5.
The interference of photoemission peaks with the NEXAFS structure shown
in Fig. 5.5b may be overcome by simply spoiling the energy resolution of the
detector. This approach was used by Wang et al. [5.23] in their NEXAFS study
of ethylene on Pd(III). By applying a triangular modulation of 50 Vat I kHz on
the dc voltage that defined the electron pass energy through the analyzer,
possible photoelectron peaks in the recorded spectrum were averaged out. In
practice, other electron yield detection methods are often used, and these will be
discussed in the following.
A fraction of the Auger electrons from the adsorbate suffer an energy loss
and emerge from the sample with a kinetic energy less than Ea. Because the
primary Auger kinetic energy is independent of hv, so is the energy distribution
of the inelastic Auger electrons shown as a hatched area in Fig. 5.4. Therefore
the inelastic Auger intensity will follow the elastic one. This fact is utilized in the
partial electron yield (PEY) detection variant where only electrons of kinetic
energy larger than a threshold energy Ep are detected (Fig. 5.4). The elastic and
part of the inelastic Auger intensity serve as the signal. By suitable choice of E p ,
one can avoid new photoemission peaks of the substrate entering the kinetic
energy window of the detector over the NEXAFS energy range. Some photo-
emission peaks may already fall into the window at the lowest photon energy of
the NEXAFS scan but this simply increases the background. It is more import-
ant to avoid new peaks entering the window because this leads to NEXAFS
unrelated structures in the spectrum as for the AEY. Because of the flexibility in
choosing E p , the PEY allows one to avoid the interference problems encoun-
tered in AEY detection. PEY measurements are best carried out with a retarding
grid detector, as discussed in detail in Sect. 5.2.4, where a negative grid
potential - E p, is used to prevent electrons with kinetic energy less than Ep from
entering the detector. It is apparent that for the same solid detection angle, the
PEY mode offers a higher count-rate than the AEY mode. However, the signal-
to-background ratio is reduced.
The third, and simplest, detection technique consists of collecting electrons
of all energies from the sample and is referred to as total electron yield (TEY)
detection. The TEY signal is dominated by low energy electrons with kinetic
122 5. Principles, Techniques, and Instrumentation of NEXAFS

energy below about 20eV (Fig. 5.4), the so-called "inelastic tail". A fraction of
the electrons comprising the inelastic tail are inelastically scattered Auger
electrons from the adsorbate and it is this fraction which is responsible for the
desired NEXAFS signal. Although the total count-rate is very large for the TEY
mode, the signal-to-background ratio is typically very small. As a rule of thumb,
for an adsorbate monolayer on a metal substrate, about 1% of the TEY signal
originates from the adsorbate. Figure 5.4 shows that the Is photoemission peak
(peak A) of the adsorbate contributes to the TEY when the photon energy
exceeds the K-shell ionization potential (i.e., the Is binding energy relative to the
vacuum level). In principle, this would lead to a step-like increase in the TEY
about 5 eV above the lowest K -shell absorption structures arising from trans-
itions to molecular bound states or substrate states near the Fermi level. In
practice, no such step is observed because the measured elastic Is photoemission
intensity increases gradually at threshold to a maximum about 20eV above the
IP [5.24] and it is small compared to the total (elastic and inelastic) Auger
electron intensity. Because of the higher kinetic energy of the elastic Auger than
the elastic photoelectrons, the K-shell TEY signal from the adsorbate is always
dominated by the inelastic Auger channel [5.25]. Thus the AEY, PEY and TEY,
except for giving different signal-to-background and signal-to-noise ratios, yield
almost identical NEXAFS spectra.

5.2.2 Quantitative Description of Electron Yield

In practice, the key issue in electron yield NEXAFS spectroscopy is to find
means of suppressing the unwanted background without jeopardizing the signal
from the adsorbate layer, i.e., optimizing the signal-to-background and signal-
to-noise ratios. Figure 5.6a illustrates the problem. Photons as shown in the
figure penetrate into the substrate composed of atoms B to a depth which is
characterized by the photon mean free path and is given by the inverse of the
X-ray absorption coefficient /lx(hv) of the material, also called the linear
X-ray absorption coefficient. This coefficient /lx(hv) [cm -1] is related to the
absorption cross section (Tx(hv) [cm 2 /atom] by the atomic volume density of the
sample nv [atoms/cm 3 ] according to

(5.2)

The volume density ~ is calculated from the mass density nm [g/cm 3 ] by the
relation ~ = nmNo/A, where No = 6.022 X 1023 [atoms/mole] is Avogadro's
number and A [g/mole] is the atomic weight. In the soft X-ray region values for
(Tx(hv) and /lx(hv) have been tabulated by Veigele [5.28] and Henke et al. [5.29].
From these data the photon mean free path 1/ Jlx(hv) in most materials at
hv = 1000 eV is of the order of 1000 A.
Absorption of X-rays leads to the creation of photoelectrons and Auger
electrons. On their way to the surface these electrons are scattered inelastically
by electron--electron and electron-plasmon interactions and quasi-elastically by
 5.2 Electron Yield Detection 123

hv hv (a)

8
t
~=Z¢za.z=~'!lL~~M1~7frz.m- Adsorbate
Atoms A

Electron~
Escape
"
"
Depth
L - 50A. ,
_L ___________ _ Substrate
Atoms B
Photon
Penetration
Depth
sin 81p.- 500 A.

J __________ _
~ 100
;S
'"
"- 50
'"
e
u.
c
'"'"
:2
c
~ 10
u
~
W
5

5 10 50 100 500 1000

Electron Energy above Fermi Level (eV)

Fig. 5.6. (a) Photo absorption and electron production in a sample consisting of substrate atoms B
and an adsorbate layer A. Only electrons created within a depth L from the surface contribute to the
measured electron yield signal. Electrons originating from layer A constitute the NEXAFS signal;
those from layer B give rise to unwanted background. (b) Electron mean free path in solids as a
function of the electron kinetic energy above the Fermi level. The shaded area represents the
distribution typically found for different materials [5.26, 27]

electron-phonon interactions. The relative importance of the scattering mech-

anisms depends on whether the material is a metal, a semiconductor or an
insulator. Nevertheless, the electron scattering length or mean free path as a
function of kinetic energy follows a "universal curve" [5.26, 27, 30] shown in
Fig. 5.6b, where the dashed region indicates the variation found in different
materials. In particular, absorption of X-rays in the range 250eV ~ hv ~ 600eV
containing the C, N, and 0 K-edges leads to primary photoelectrons and Auger
electrons with mean free paths typically less than 10 A. The inelastic scattering of
these primary electrons results in an electron cascade as shown in Fig. 5.6a.
When the cascade reaches the surface only those electrons will escape into
vacuum which have sufficient energy to overcome the surface potential barrier.
This limits the origin of the TEY signal to an effective escape depth L since
electrons generated deeper inside the sample will have insufficient energy to
escape.
124 5. Principles, Techniques, and Instrumentation of NEXAFS

The value of L has been estimated by Gudat [5.31] in the 50-150eV spectral
range to be less than 50 A for metals and semiconductors and by Jones and
Woodruff [5.32] to be 65 A for aluminum metal and 130 A for aluminum oxide
at hv ~ 1600eV. The two latter numbers illustrate the fact that L is typically
longer in insulators (e.g., A1 2 0 3 ) than in semiconductors and metals (e.g., AI)
owing to the reduced electron-electron scattering mechanism at low kinetic
energy in insulators. To understand how the surface signal can be enhanced and
the background signal reduced let us consider their dependence on physical
parameters.
The AEY signal from the adsorbate layer with atomic area density pA,
K-shell cross section (1~, and nonradiative Auger yield w~, emitted into a solid
angle Q, is given by [see (5.1)]

I~(hv) = ~ IoAo(1~(hv)pAw~ . (5.3)

Here we have again assumed that the fraction of X-rays absorbed in the
adsorbate layer is small, i.e., (1~ pA ~ 1. We have explicitly indicated that the
NEXAFS structure arises from photon energy dependent modulations in
(1~(hv ).
Rigorous calculation of the electron yield from the substrate is difficult
because of the complexity of the electronic scattering and cascading processes.
In principle, it would be desirable to write down a general expression for the
electron yield as a function of the photon energy, the electron kinetic energy, the
X-ray incidence angle, and the electron emission angle. The TEY, PEY and AEY
would then be obtained from this expression by integration over the appropriate
kinetic energy range and detector acceptance. Unfortunately, such a general
theory does not exist at present and we shall therefore discuss an approximate
theory for the TEY and use it to explain the surface sensitivity enhancement in
the PEY and AEY detection modes.
For the TEY, we use a simple model that averages over the various
complicated electron scattering processes and describes them by effective para-
meters with physical meaning. Our model follows Fig. 5.6a and describes the
interaction of the X-rays with the bulk sample by an absorption coefficient
J.l~(e, hv) where e is the X-ray incidence angle on the sample measured from the
surface. The so-defined absorption coefficient includes the effects of X-ray
refraction at the surface and is in general obtained from the optical constants
[5.29, 33, 34]. However, in the soft X-ray region at sufficiently large incidence
angles (> 10°) we can neglect reflection and refraction [5.35] and express
J.l~(e, hv) in terms of the tabulated [5.28, 29] absorption coefficient J.l~(hv), see
(5.2), according to

B J.l~(hv)
[Link](e, hv) = -.-e-· (5.4)
sm

Equation (5.4) expresses the fact that absorption is geometrically enhanced, and
 5.2 Electron Yield Detection 125

the beam penetration into the sample shortened, at nonnormal X-ray incidence
angles (Fig. 5.6a). The number of photoelectrons created in the sample at a depth
z, within an increment dz, is given by

N~ = IoAoJl~(lJ, hv)e -1'~(8,hv)z dz . (5.5)

We have neglected the reflection of the X-ray beam at the surface which would
contribute a factor 1 - R(lJ), but at the photon energies and X-ray incidence
angles of interest here, the reflectivity R(lJ) is negligibly small [5.29]. The
primary electrons created propagate to the surface by inelastic scattering
processes and the creation of low-energy secondary electrons which, according
to Fig.5.6b, have the longest mean free paths. We describe the various
energy-dependent electron scattering lengths simply by an effective electron
scattering length L e , which is largely determined by the mean free paths 1; of the
low-energy secondaries according to I/Le = 1:(1/1;) and is, to first order, inde-
pendent of the photon energy. The multiplication and loss of electrons, their
transport to the surface and escape into vacuum is described by a single electron
gain function Ge(hv).
Experiment and theory [5.36-39] both show that for a given material the
shape of low-energy electron distribution ("inelastic tail") is independent of the
primary electron energy once it is higher than about 20eV. The distribution is
well described by the function Ek/(Ek + cjJ )4, where Ek is the kinetic energy
relative to the vacuum level and cjJ is the work function [5.38, 39]. On the other
hand, the number of low-energy electrons increases linearly with the primary
energy, i.e., with the photon energy. We can therefore write for the total gain
Ge(hv) = hvM, where M is a material constant describing the conversion effici-
ency into low-energy electrons. In analogy to the attenuation of X-rays de-
scribed by the exponential factor in (5.5), one can interpret the quantity 1/Le as a
linear electron-attenuation coefficient and mathematically describe the electron
scattering processes as the attenuation of a single electron multiplied by a gain
factor hvM. The primary electron generated in the increment dz inside the
sample then contributes a fraction dI~ to the TEY, emitted into a solid angle D,
given by

D
dI~ = 41t N~ e- z /L hvM . (5.6)

Here we have defined the effective electron escape depth L as the projection of Le
along the surface normal. Integration of(5.6) over the sample thickness gives the
TEY signal generated in the sample. If we assume that the sample is much
thicker than both the X-ray penetration depth sin lJ / Jl:Ahv) and the effective
electron escape depth L, we obtain for the TEY signal of the substrate [5.31]

B D Jl~(lJ, hv)
It (lJ, hv) = 41t IoAo Jl~(lJ, hv) + I/L hvM . (5.7)
126 5. Principles, Techniques, and Instrumentation of NEXAFS

The dependence of the TEY on the X-ray incidence angle (J is contained in the
ratio factor in (5.7).
For the following discussion we shall define for brevity Jl8 =
Jl~«(J, hv) = Jl~(hv)/sin (J. At more grazing X-ray incidence angles (J, the effective
X-ray absorption coefficient Jl8 increases and the ratio in (5.7), which can be
rewritten as Jl8L/(Jl8L + 1), approaches 1 in the limit LJl8 ~ 1. Thus at grazing
incidence angles the TEY is strongly enhanced and it is no longer proportional
to the X-ray absorption coefficient. This has been observed experimentally by
Gudat [5.31] and Martens et al. [5.40]. The physical reason for this effect is that
all X-rays are absorbed in a surface layer with thickness 1/ Jl8 ~ L and the
electron signal saturates. The only energy-dependent modulation of the electron
yield arises from the term Jl~«(J, hv). In the limit Jl8L ~ 1, which is fulfilled at
larger X-ray incidence angles, we obtain Jl8L/(Jl8L + 1) ~ Jl8L and the TEY is
proportional to the X-ray absorption coefficient. This was first pointed out by
Lukirskii [5.41] and Gudat and Kunz [5.42] and has been extensively utilized in
recording EXAFS spectra of bulk materials [5.25,43-45].
For a given substrate, values for Land M can be obtained from measure-
ment of the quantum yield yg, defined as the number of electrons emitted
(0 = 2n) per incident photon. Typically yg is measured at normal X-ray
incidence, (J = 90°, such that Jl8L ~ 1, and with this approximation we obtain
from (5.7)

B l~(hv) 1 B
Yo(hv)=--=-2 Jlx (hv)LhvM. (5.8)
loAo

Henke [5.46] has demonstrated the usefulness of (5.8) for the description of the
photon energy dependence of the quantum yield for several materials. From his
plots we obtain the quantum efficiencies of Au at hv = 300eV to be 6.5 x 10- 2
and 4.5 x 10- 2 at hv = 1500eV. Using tabulated values for Jl~(hv) [5.28] we can
calculate the product LhvM from (5.8) and obtain the values 42A (300eV) and
210A (1500eV). The ratio between the numbers is exactly that of the photon
energies, indicating that the product LM (=0.14A eV- 1 ) is independent of
photon energy, as assumed in the derivation of (5.7). The most direct way to
obtain the conversion efficiency M, and therefore L, is to measure the electron
gain Ge(hv) = hvM of the substrate directly. This is simply done by simultan-
eous measurement of the TEY with a pulse counting electron multiplier and a
current amplifier. Since all electrons from the same primary absorption process
reach the electron multiplier within a time interval ( < 10- 13 s) that is short
relative to the detector response time they will contribute to the same mUltiplier
pulse. The ratio of electron number yield obtained from the current measure-
ment to the pulse number yield is then equal to the number of electrons
produced inside the sample per primary electron, i.e., equal to the gain hv M.
Using the data for Au obtained by Eliseenko et al. [5.47] with AI-K.. (1487 eV)
radiation, Henke et al. [5.38] have obtained the value hvM = 4.3. Thus at
hv = 1487 eV each primary electron produces 4.3 electrons on the average. At
 5.2 Electron Yield Detection 127

hv = 300eV, we obtain hvM = 0.87 and there is no gain but rather a small loss
in the transport and emission process. Combination of these results with the
values for Lhv M obtained earlier gives the electron escape depth in Au as
L = 50 A, independent of hv in the 300-1500eV region. This value is in excellent
agreement with the values found for metals by Gudat [5.31] and Jones and
Woodruff [5.32].
An expression for the PEY signal I:(lJ, hv) from the substrate can be
obtained by suitable modification of(5.7). Because in PEY detection low-energy
electrons are eliminated, the electron gain hvM inside the substrate is equal to 1.
Furthermore, the effective electron escape depth L is greatly reduced according
to Fig. 5.6b such that the approximation f.l8L ~ 1 is valid for typical X-ray
incidence angles (lJ ~ 10 0) and we obtain

(5.9)

It is difficult to write down an expression for the electron signal from the
substrate when the AEY from the adsorbate is monitored. This would require
calculation of the inelastic photoelectron signal of the substrate at the energy of
the adsorbate Auger peak (Fig. 5.5a). As a rule of thumb, one would expect it to
be less than half of the PEY signal because the elastic photoemission peaks of
the substrate do not directly contribute (Fig. 5.5).

5.2.3 Adsorbate Versus Substrate Signal

We are now in a position to estimate the signal-to-background ratio SB obtained
in an electron yield measurement of a chemisorbed molecular layer on a
substrate. We assume that the adsorbate signal is given by the AEY (5.3). This
neglects any secondary electrons created by scattering of elastic Auger electrons
(Fig. 5.4) and therefore underestimates the adsorbate signal. We could compen-
sate for this loss by introducing a gain factor for the adsorbate signal which,
similar to that of the substrate, would be proportional to hv. It is simpler,
however, to account for this effect by eliminating the gain factor hvM from the
expression for the substrate signal, instead. Furthermore, we assume that
f.l8L ~ 1, which is valid for measurements at larger X-ray incidence angles
(Fig.5.6a). Both PEY and TEY signals are then described by (5.9), but with
different escape depths L, and the signal-to-background ratio is given by

S _ (1~(hV)pAQ)~
(5.10)
B - f.l~(lJ, hv)L

With the values appropriate for a monolayer of C atoms at hv = 300eV,

(1~ = 9 x 10- 19 cm 2 /atom [5.28], pA = 10 15 atoms/cm 2 , and Q)~ = 1 and those
for a Au substrate at the same energy f.l~ = 3 X 10- 3 A -1 [5.28], and L = 50A
we obtain SB = 6 X 10- 3 for TEY detection. For PEY detection L is shortened
128 5. Principles, Techniques, and Instrumentation of NEXAFS

to about S A according to Fig. S.6b and therefore SB is increased by an order

of magnitude.
The above estimates are for a Au substrate, which has a large absorption
coefficient, and therefore electron yield, in the 300-1000eV spectral range. For
example, relative to Au the absorption coefficients for other substrates at 300eV
are lower by factors 4.5 (Si), 3.S (Ag) and 2.2 (Cu) [S.28, 29] and therefore larger
signal-to-background values would be observed. We therefore expect typical SB
values of 1-2% for TEY, 10-20% for PEY, and > 20% for AEY measurements
for a chemisorbed monolayer. These numbers are in good accord with experi-
mental observations of typical signal-to-background ratios or edge jump ratios
in SEXAFS spectra of chemisorbed atoms [S.4S].
From (S.10) the dependence of SB on photon energy is determined by the
ratio (J~(hv)/ Jl~((}, hv). Since both quantities decrease with photon energy one
would expect to measure approximately the same SB values for carbon (K -edge:
28SeV) and sulfur (K-edge: 2470eV) monolayers on the same substrate. This is
in fact the case [S.4S] and, in retrospect,justifies the neglect ofthe gain factor in
(S.10). If we had not eliminated it, the increase in hvM from C (0.87) to S (7.5)
would have resulted in an unrealistically small SB value for a chemisorbed S
layer. This indicates that in reality both the substrate and the adsorbate TEY
signals increase with hv because of the contributions from their low-energy tails.
Another method which allows further reduction of the bulk background is
based on geometry and consists of detecting electrons at grazing emission
directions from the surface. Full appreciation of this effect requires an under-
standing of electron refraction at the surface. To escape into vacuum, an electron
has to overcome a surface potential barrier. The electron travelling in a free
electron band state crosses the surface conserving the parallel wave vector
component while the component normal to the surface alters because of the
kinetic energy required to overcome the barrier [S.48]. The refraction at the
surface can be expressed in terms of the surface barrier Vo, i.e., the energy
difference between the vacuum level and the bottom of the free-electron-like
conduction band, and the kinetic energy Ek of the electron measured from the
vacuum level. Note that Vo is not the work function, but the work function plus
the separation of the Fermi level from the bottom of the free-electron-like bands.
Electrons at the Fermi level already have kinetic energy and the work function is
simply the minimum energy needed to excite these electrons into vacuum.
Electrons approaching the surface at an angle IX from the inside surface normal
are refracted into vacuum at an angle (j from the outside surface normal
according to [S.49]

sin (j = (
E
k
+ V.
Ek °)1/2 sin IX • (S.11)

At a given kinetic energy only electrons which approach the surface inside
the crystal within a momentum cone (often called a "primary Mahan cone")
[S.48] centered around the surface normal can escape; those outside the cone do
 5.2 Electron Yield Detection 129

not have enough perpendicular momentum and are reflected back into the solid.
The maximum cone angle IXmax> corresponds to sin!5 = 1 in (5.11), i.e., when the
escaping electron emerges from the surface at !5 = 90°. The largest refraction
angle is 45° and occurs for c5 = 90° and Ek = Vo. For example, Williams et al.
[5.49] showed that for Cu Vo = 14eV, such that at Ek = 100eV the maximum
cone angle is IXmax = 70 ° and therefore refraction angles are as large as 20°, even
at this high kinetic energy.
Applying (5.11), we can now express the effective electron escape depth
Le cos IX inside the crystal as a function of the measured angle c5 outside the
crystal and obtain

L = Le ( Ek cos 2 !5 + Vo )1/2 (5.12)

Ek + Vo Ek + Vo
For PEY and AEY detection, only high energy electrons are detected and with
Ek ~ Vo refraction at the surface can be neglected. In this case the effective
escape depth L is reduced by a factor cos IX ~ cos!5 and therefore SB (5.10), is
increased by a factor 1/cos!5. This surface enhancement by grazing incidence
electron detection has in fact been extensively utilized in X-ray photoelectron
spectroscopy [5.50].
Finally, the background from the substrate can be reduced by proper choice
of the detector position relative to the electric field vector E of the polarized
X-ray beam. As discussed in detail in Chap. 9, synchrotron radiation is approxi-
mately linearly polarized with the E vector in the horizontal orbit plane of the
storage ring. By Yang's theorem [5.51], dipole excitation of a photoelectron in a
randomly oriented system leads to an angular distribution of the form

da(Ek' Y)
dQ
= a(Ek)
4n
(1 + peEk) (3
2
2
cos y
_ 1)) , (5.13)

where y is the angle between E and the electron emission direction, and Pis the
photoelectron asymmetry. Measurements and calculations of the energy de-
pendence of the photoemission cross section a(Ek) and peEk) are fairly abund-
ant for gases [5.52] and, depending on the atomic level and energy, peEk) varies
between -1 and 2. It has been recognized by Davis et al. [5.53] that photo-
electron asymmetry effects also exist for solid samples and, most importantly,
that in all studied cases the measured angular distributions showed a tendency
toward high asymmetry, characterized by P= 2. If we accept this result, (5.13)
becomes

(5.14)

and the photoemission intensity is peaked in the direction of E. This has

important consequences since by choosing a detector acceptance geometry 90 °
from the E vector, most of the photoemission intensity is eliminated. Since the
130 5. Principles, Techniques, and Instrumentation of NEXAFS

photoelectron signal constitutes a large fraction of the total electron intensity

from the substrate the background can be significantly reduced using the
photoelectron asymmetry effect.

5.2.4 Experimental Details and Detectors

A typical experimental arrangement for electron yield NEXAFS studies is
shown in Fig. 5.7. The X-ray beam from the monochromator is first collimated
by a set of moveable blades and then falls onto a metal grid with about 100
wires/cm and a transmission around 80%. The TEY signal from this grid,
amplified by a channeltron or spiraltron [5.54, 55] electron multiplier, serves as
a dynamic reference monitor of the X-ray intensity. The grid can be coated in
situ by evaporation of a suitable metal which does not have any absorption
edges in the energy range of interest. When the signal from the grid is only used
to normalize out fluctuations in the X-ray intensity emitted by the storage ring
(and not the energy dependent transmission function of the beam line optics, see
Sect. 5.5) it is often convenient and advantageous to simply use a "dirty" gold
grid. Because of its noble metal character, gold is typically covered with only a
monolayer of carbon and oxygen adsorbates whose K-edges are barely visible in
TEY detection. The stability of such a grid with respect to time coupled with its
high and rather smooth quantum efficiency make it an ideal reference monitor in
the soft X-ray region.

.....-t:.,
X-Ral/s......

~EII
~ Electron Multipl ier
II fEvaporator
Partial Yield
Detector

Fig. 5.7. Experimental arrangement for electron yield NEXAFS studies. The elliptically polarized
X-ray beam from the monochromator, with the major electric field vector component Ell in the
horizontal plane, is collimated and then transverses an in situ coatable metal grid which, in
conjunction with an electron multiplier, serves as a dynamic reference monitor. Electrons from the
sample are detected either by an electron energy analyzer such as the shown cylindrical mirror
analyzer (eMA) or a partial yield detector. This detector is shown in more detail in Fig. 5.9 and can
also be used for total electron yield detection by proper bias of its two metal grids. A phosphor
coated screen in the beam path serves for alignment purposes
 S.2 Electron Yield Detection 131

...
f
]:.~;:.~~~
Metal
To
Scaler

Grid

HV Power Supply
Fig. 5.8. Measurement scheme for total yield collection from a metal grid reference monitor.
The electron signal is amplified by a channeltron electron multiplier which is operated at voltages
VI"" + SOV and V2 "" + 2000 V, respectively. The amplified electron output current is collected by
a collector plate kept at V3 > V 2 by means of a high voltage battery box (2 kV ::::; V3 ::::; 3 kV). The
negative side of the floating battery box is connected to a current amplifier capable of monitoring
currents in the 10- 1°-10- 8 A range. Avoltage (0-10 V) signal proportional to the input current is
then fed into a voltage-to-frequency converter which is read by a computer via a data scalar

The electronics associated with the measurement of the TEY current from
the grid is shown in Fig. 5.8. Electrons from the grid, kept at ground potential,
are pulled into the channeltron cone by a small positive voltage (V 1 ~ 50 V).
Assuming a channeltron gain factor of 106 , one incident electron per second
results in a channeltron output of 106 e1ectrons/s or a current of 10- 13 A. Thus
current measurement techniques can conveniently be used. This is accomplished
most easily by use of a floating battery box which supplies a low-noise positive
bias potential (V 3) in the 2-3 kV range to the collector of the channeltron. The
high potential is generated by a series of ~ 300 V batteries which are suitably
insulated from each other and the battery box housing and soldered together to
eliminate noise. The achievable noise level is limited by leakage currents and is
about 10- 11 A. The negative side of the battery string is connected to the input
of a current amplifier (and therefore is close to ground potential) which gener-
ates an output voltage proportional to the input current. The signal (voltage) is
then converted to a frequency and fed into the scaler of a computer.
The signal from the sample is detected either by an electron energy analyzer
such as the often used and commercially available cylindrical mirror analyzer
(CMA) [5.56] or by a simple partial yield detector (PYD). Other electron
analyzers have been reviewed by Smith and Kevan [5.57]. As shown in detail in
Fig. 5.9, a PYD is easily built and assembled using two high transmission metal
grids for retardation and a double channel plate assembly for electron multipli-
cation [5.54]. Typically the first grid is operated at ground potential and the
second grid at a retardation voltage - Ep where Ep is the PEY cutoff energy
defined in Fig. 5.4. Suitable cutoff energies for PEY studies of low-Z atoms are
~ 180-230eV for carbon, ~ 290-340eV for nitrogen, and =::: 430-480eV for
oxygen, such that the corresponding Auger peaks around 260eV (C), 370eV (N),
132 5. Principles, Techniques, and Instrumentation of NEXAFS

Portia I [telCtron Yield [Link] Fig. 5.9. Assembly drawing of a double-channel plate

©
partial electron yield detector. All components are as-
Coverplote
sembled in the depicted order in the ceramic housing

g Compression
Spring
shown at the bottom. The electrons entering the detector
first traverse a metal grid typically kept at ground poten-

© Ceramic
Spacer
tial (V, = 0), and low energy electrons are then elimina-
ted by a second grid kept at a negative retarding voltage
v,
~ ht Metal Grid (V 2 ) . Typical retarding voltages are -2OOV for carbon,

©
- 320 V for nitrogen, and -450V for oxygen K-shell
CClromlc
Space,. measurements. The electron signal is amplified by a dual
channel plate arrangement. The channel plate voltages are
v,
~ 2nd [Link] Grid supplied by metallic ring contacts. Typical values are

©
V 3 ", + 30V, V 4 ", + 1000 V, and V s '" +2000V. The dual

--
Ceramic
Spoc.,.. channel plate arrangement operates at a total gain of
v,
©' Ring Contact

1sf Channel Piol.

10 7_ 108 and the electron output is collected by a collec-
tor which is connected for current measurement to a
floating battery box as shown in Fig. 5.8. The collector
voltage V6 is kept somewhat ('" + 100 V) larger than VS
V.
©b Ring Contoct

2nd Channel Plat.

~
V. RIng Contact

© Ceramic
Spacer

V.
£::) [Link]

ffi Ceramic
HaUling

and 510eV (0) fall in the detection window. By using a slightly positive bias
potential on the two grids ( ~ 10-20 V), the PYD can also be used for total
electron yield measurements.
The acceptance angle of PYDs can be made quite large, of the order of
10-20% of 4n sr, either by positioning it close to the sample or by using large
channel plates. In comparison, the acceptance of the CMA is about 7% of 4n sr.
The detector efficiency, defined as the ratio of the number of detected to incident
electrons, is determined by the electron optics only, since typical electron
multipliers have unit detection efficiency for electrons with kinetic energies in
the hundred eV range. PYDs typically have ~ 80% grid transmission and
therefore detection efficiency. For a double pass CMA the overall efficiency is
about 5% [5.56]. Typically the output signal from the CMA or the PYD is large
enough that current measurement techniques can be employed (Fig. 5.8).
The phosphor covered screen (Fig. 5.7) is a very useful device for alignment
of the X-ray beam in the chamber and for alignment of the sample in the beam.
In particular, at grazing X-ray incidence a slight misalignment of the beam will
cause it to generate a signal from the edge of the sample, which in a polarization
 5.3 Fluorescence Yield Detection 133

dependent study may lead to an incorrect determination of the molecular

geometry on the surface. Since the front surfaces of typical single crystal
substrates are polished, they reflect the soft X-rays at small incidence angles and
the reflected beam can be monitored on the phosphor screen for alignment
purposes. Also one may simply watch the shadow image of the sample in the
beam spot on the phosphor screen.

5.3 Fluorescence Yield Detection

In considering the detection of the fluorescent X-ray signal from a thin adsorb-
ate layer on a bulk substrate it is important to understand all interactions of the
incident X-rays with the sample that result in "secondary" photons. These are (1)
X-ray absorption followed by fluorescence decay, (2) coherent and incoherent
scattering of X-rays from the bulk substrate, (3) specular reflection of X-rays,
and (4) diffuse scattering by surface irregularities. In a theoretical treatment it is
convenient to discuss separately bulk-dominated effects such as X-ray absorp-
tion and scattering versus "surface" effects such as reflection and diffuse
scattering. This is done below.

5.3.1 Absorption and Scattering of Soft X-Rays

The relative cross sections of X-ray absorption and scattering, taken from the
work of Hubbell et al. [5.58], are shown in Fig. 5.10 for a copper (Z = 29) target.
The dominant interaction of soft X-rays with matter is by means of photoelectric
excitation, i.e., X-ray absorption, whose cross section U x is orders of magnitude
larger than the coherent scattering cross section ues • In a coherent scattering

Cu (Z=29)

Fig. S.10. X-ray cross sections for differ-

----- ......,
Des

,, ent interactions with a copper (Z = 29)

atom [5.58]. (f x is the photoelectric or X-
ray absorption cross section, (f" is the
-~.
coherent (Rayleigh) scattering cross sec-
,/ \~
Oil '\ tion, (fi. is the incoherent (Compton)
scattering cross section, (f ""ir is the cross
/ section for pair production, and (fn",,' is
the nuclear photoabsorption cross sec-
tion. The total cross section (ftot is the
Photon Energy (eV) sum of all others
134 5. Principles, Techniques, and Instrumentation of NEXAFS

event, also called Rayleigh or elastic scattering, a photon is scattered by an atom

without change of its wavelength. Incoherent scattering, also called inelastic or
Compton scattering, is characterized by a change in X-ray wavelength and is
very weak in the soft X-ray region with a cross section a i • that is orders of
magnitude smaller than a c•• Therefore we can neglect it altogether. We note,
however, that at high X-ray energies inelastic scattering becomes relatively large
(Fig. 5.10), and "photon energy loss" or "X-ray Raman" spectroscopy has in fact
been used to record the K-shell excitation spectrum of diamond [5.59].
The maximum K-shell X-ray absorption cross sections of the low-Z elements
in the 200-2500eV range and the energy-dependent X-ray absorption cross
sections of copper and gold, taken from the tables compiled by Veigele [5.28],
are plotted in Fig. 5.11. For the low-Z elements important data for K-shell
excitations are summarized in Table 5.1, such as the X-ray absorption cross-
section above (a::,aX) and below (a::'in) the K-edges, the edge jump ratio
J R = a::,ax/a::,in and the fluorescence yield wf'
Veigele [5.28] also lists coherent scattering cross sections in the soft X-ray
range but they have been derived by extrapolation and are not very accurate. In
particular, they neglect the strong dispersion effects (anomalous scattering)
occurring near the various absorption edges in the soft X-ray region. The
coherent scattering cross sections can be calculated, however, from the real part
11 and imaginary part 12 of the complex atomic scattering lac tors 1=11 + iI2
tabulated by Henke et al. [5.29] for the elements in the 100-2000 eV region.

Fig. 5.11. Soft X-ray photoelectric

(absorption) and coherent scattering cross
sections for selected elements. The photo-
electric cross sections for the K -shells of
the low-Z atoms boron (Z = 5) through
sulfur (Z = 16) are taken from the tables of
Veigele [5.28]. For the low-Z atoms the
maximum cross sections just above the K-
edge are plotted. For carbon, fluorine,
magnesium and phosphorus the jumps
/ / - - - - - - - - - - . . . . Au through the K-edge are also shown. The
coherent scattering (Rayleigh) cross sec-
I
tions for carbon, copper and gold were
~r-CU calculated by means of (5.16) using the
atomic scattering factors tabulated by
Henke [5.29]. Note that the so-obtained

"' ir'-'-'-'-'-'-'-
K-edge I cross section for copper agrees in magni-
C tude with that plotted in Fig. 5.10 but in
addition exhibits an anomalous dispersion
1011::!-.L-I-.I...I:-!+.J...L-!-::,:~~,*:!~~~L.J....~
1000 1500 2000 2500 effect near the L3 (-930eV) and L2
Photon Energy (eV) (-950eV) edges
 5.3 Fluorescence Yield Detection 135

Table 5.1. Cross section, edge jump ratio, and fluorescence yield for K-shell excitation of low-Z
atoms

Atom 2 max"
(5,
min"
(5, JR JR WI Wft1~ax

[10 5 b] [10 5 b] theory' exp.b [x 10- 2 ], [Wb]

B 5 14.7 0.66 22.3 28.5 0.17 2.5

C 6 9.8 0.51 19.2 24.3 0.28 2.7
N 7 6.9 0.39 17.7 21.3 0.52 3.6
0 8 5.1 0.33 15.5 19.1 0.83 4.2
F 9 3.9 0.28 13.9 17.4 1.3 5.1
Ne 10 3.2 0.24 13.3 16.0 1.8 5.8
Na 11 2.9 0.20 14.5 14.9 2.3 6.7
Mg 12 2.4 0.17 14.1 13.9 3.0 7.2
Al 13 2.0 0.15 13.3 13.1 3.9 7.8
Si 14 1.7 0.14 12.1 12.4 5.0 8.5
P 15 1.5 0.13 11.5 11.8 6.3 9.5
S 16 1.3 0.12 10.8 11.3 7.8 10.1

• [5.28]
b Calculated by use of the empirical formula JR = (125/2) + 3.5, given in [5.28]
, [Ref. 5.12, Table 3]

Using the relationship A = 2nhc/(hv) we obtain the relation

A A _ 12398.52
[ ] - hv[eV] , (5.15)

linking X-ray energy hv (units: eV) with X-ray wavelength A (units: A). Therefore
in the soft X-ray region the wavelength is much larger than the atomic diameter.
In this long wavelength limit, the cross section for coherent scattering from an
atom with scattering factors II and 12 is given by

(5.16)

where re = e 2 /mc 2 IS the classical electron radius and 8nr; /3 =

0.665 x 1O-24 cm 2 is the Thomson cross section. Equation (5.16) has been
derived from the basic theoretical expressions given by Warren [5.60] and is
valid for linearly polarized as well as unpolarized light, see (5.30). We have
plotted G"cs for carbon, copper and gold in Fig. 5.11 to demonstrate its depend-
ence on Z and for comparison with the respective X-ray absorption cross
sections. The elastic scattering cross sections are only plotted up to 2000eV
since Henke's tables do not list values for II at higher energies. Also, at higher
energies the long wavelength approximation assumed in the derivation of (5.16)
is no longer valid [5.29, 60, 61].
As discussed above, the coherent scattering cross section calculated from
(5.16) includes dispersion effects and therefore differs in its energy dependence
136 5. Principles, Techniques, and Instrumentation of NEXAFS

from that typically found in the tables [5.28]. This can be seen by comparison of
the copper cross sections (leo plotted in Figs. 5.10 and 5.11. Note, however, that
there is good agreement of the magnitudes in nonresonant energy regions. The
coherent scattering cross section varies significantly with Z and is about two
orders of magnitude higher for gold than for carbon. The maximum K -shell
photoelectric cross section decreases by about an order of magnitude between
boron (Z = 5) and sulfur (Z = 16) but it is still almost two orders of magnitude
higher for sulfur than the largest coherent scattering cross section value, that of
gold. It should be noted that the X-ray absorption cross section (Ix is related to
the imaginary part of the atomic scattering factor according to

(5.17)

where C = 2rehc = 7.0 x 10- 17 eV cm 2 . The (Ix values obtained with the f2
values of Henke et al. [5.29] are in good agreement with those tabulated by
Veigele [5.28]. Using the cross sections plotted in Fig. 5.11 we can now calculate
the fluorescent and scattered X-ray signals from the substrate atoms.
The theoretical description of the fluorescence yield from the bulk substrate
is somewhat simpler than that of the electron yield because X-rays interact less
strongly with matter than electrons. Hence the complicated inelastic scattering
processes of the photoelectrons on their way out of the substrate are nonexistent
for the fluorescent photons, or at least so small that they can be completely
neglected. We only need to take absorption of the fluorescent radiation into
account. In analogy to (5.6), we can write for the fluorescence signal dl' created
in the substrate at a depth z, within an increment dz,

d/B(hv)
f
= !!..- I A IIB«() hV)WB e -I'~(/J,hv)z e -
4n 0 0 r x ' f
zID(Ej) dz
'
(5.18)

where we have assumed that the fluorescence yield from the substrate can be
characterized by its strongest component w"
which occurs at an energy Ef'
D(Ef ) is the effective X-ray escape depth at the fluorescent energy, measured
along the surface normal. If the fluorescent radiation is detected at an angle h
from the surface normal, the X-ray escape depth is related to the X-ray
absorption coefficient according to D(Ef ) = cos h/ flx(Ef)' By integration over the
sample thickness, and assuming that the sample is much thicker than both
1/ fl~«(), hv) and D(Ef)' we obtain

B Q fl~«();hv)w'
If«(),hv) = 4n loAo fl~«(),hv) + l/D(Ef ) . (5.19)

The coherent scattering contribution from the substrate is derived in a

similar fashion to the fluorescence contribution, considering an X-ray absorp-
tion coefficient fl~«(), hv) en route to the scattering center inside the sample, an
effective X-ray escape depth D(hv), and integrating over an infinitely thick
 5.3 Fluorescence Yield Detection 137

sample. We obtain

B Q CT~.n~
Ic.«(J,hv) = 4n 10Ao Ji~«(J,hv) + I/D(hv) , (S.20)

where n~ (atoms/cm 3 ) is the volume density of the substrate and CT~. is given by
(S.16).
It is important to note that in the soft X-ray region Bragg scattering typically
does not exist. From the Bragg equation A = 2d sin (J, we know that the longest
Bragg-scattered wavelength is given by Amax = 2d, and since almost all natural
crystals have d-spacings ofless than 2 Awe see that Amax ~ 4 A, corresponding to
a minimum photon energy for Bragg scattering of about 3000eV.

5.3.2 X-Ray Reflection and Diffuse Scattering

In detecting photons from the sample one also needs to consider the intensity of
the reflected X-rays. Although the specular reflectivity is very low for incidence
angles larger than 10 typically used in NEXAFS studies, the high incident flux,
0

of the order of 10 10 photons/s, leads to a significant reflected signal which, when

directed into the detector, may dominate the fluorescence signal. Below we
consider the size of the angle-dependent X-ray reflectivity of a metal substrate in
the 2S0-2000eV spectral range.
The X-ray reflectivity of a material is calculated by means of the Fresnel
equations. We shall use here a formalism developed by Stern [S.62] and Heavens
[S.63] for the reflectivity at the interface between two homogeneous layers. By
defining (J as the grazing angle of incidence from the surface, ko, the component
of the incident wavevector perpendicular to the surface (in vacuum) is given by

2n. (J
ko =ysm (S.21a)
,

and k1 (the tilde denotes complex numbers), the wave vector component perpen-
dicular to the surface in the substrate, can be calculated according to

k-1 = Y2n J-8 1 - cos 2(J . (S.21b)

Here Ais the wavelength of the incident radiation in vacuum and 81 the dielectric
constant of the substrate, which can be calculated from the atomic scattering
factors 11 and 12 [S.29] according to

8-1 -_1_
re A2nV(r
)1 - 1·f)
2 . (S.22)
n
where re = 2.82 x 10- 13 cm is the classical electron radius and nv is the number
of atoms per unit volume in the substrate with atomic scattering factors 11
and 12.
138 5. Principles, Techniques, and Instrumentation of NEXAFS

We next consider the specular reflectivity. We denote as rm the reflection

coefficient at the interface between vacuum and substrate. The polarization
direction of the electric field vector E is characterized by the label m. For s-
polarized light, m = s, and E is perpendicular to the plane of incidence, i.e.,
parallel to the surface of the specimen, while for p-polarized light m = p, and E
lies in the plane of incidence. The Fresnel equations then define the polarization
dependent reflection coefficients at the vacuum-substrate interface in terms of
the wave vector components ko and k1 and the dielectric constant 81 according to

(5.23)

and
_
=
81 ko - k1
_ .
rp (5.24)
61 ko + k1
The measured specular reflectivity is obtained as
(5.25)

where Ro((J) is the Fresnel reflectivity of the perfectly smooth surface and the
asterisk denotes the complex conjugate. The exponential term accounts for a
finite surface roughness characterized by a root mean square (RMS) roughness ()
perpendicular to the surface [5.64].
Calculated reflectivities Ro((J) for gold and copper at 277 eV(C K Il ) and
2042 eV(Zr LI%) for an s-polarization geometry are shown in Fig. 5.12. For p-
polarization, the reflectivity near the extreme incidence angles (lJ = 0° or 90°) is
identical to that in s-polarization but exhibits a pronounced minimum at the
Brewster angle near lJ = 45 ° [5.65]. In particular, for linearly polarized radi-
ation the Fresnel equations show that the p-reflectivity is equal to the square of
the s-reflectivity at lJ = 45° and therefore extremely small. Figure 5.12 also
illustrates the dramatic effect of surface roughness by showing a reflectivity
curve calculated for a gold surface with () = 20 A vertical roughness at 277 eV.
This curve drops by 7 orders of magnitude as the X-ray incidence angle from the
surface is increased to 30°.
Elastic scattering processes occur not only in the bulk but also at the surface.
A real surface can be described by a distribution of structures with aRMS
roughness () perpendicular to the surface and a lateral correlation length A
characterizing the average separation of the structures parallel to the surface
[5.64]. This surface roughness influences the reflectivity when the phase differ-
ence of beams reflected at different points of the surface becomes large. In this
case the specularly reflected fraction R(lJ) is reduced according to (5.25) and an
"incoherent" fraction, called diffuse scattering. is created. The scattered radiation
is spatially incoherent but temporally coherent, i.e., it is of the same wavelength
as the incident radiation. If we neglect absorption by the surface, the diffuse
 5.3 Fluorescence Yield Detection 139

Fig. 5.12. Calculated reflectivities Ro(lI)

z for perfectly smooth copper (dotted curves)
and gold (solid curves) surfaces at 277 eV
(carbon K.) and 2042eV (zirconium L.).
The assumed geometry (s-polariz-
y
ation) is shown as an inset. Also shown
is a curve calculated with (5.25) for
hv = 277 eV assuming a gold surface with
a RMS vertical roughness () = 20 A. Here
K = 41t sin 11/). is the momentum transfer
upon reflection

--Au
.......... Cu

o 10 20 30 40 50 60 70 80 90
Incidence Angle 8 (deg)

scattering intensity integrated over all angles, called total integrated scatter, is
simply obtained as the difference of the intensity reflected by the perfectly
smooth and the rough surface, and is given by [5.66]

(5.26)

5.3.3 Adsorbate Fluorescent Signal and Substrate Background

Because of the low scattering cross section for low-Z atoms we can neglect the
elastically scattered radiation from the adsorbate layer. The X-ray fluorescence
signal INhv) from the adsorbate is given by an expression similar to (5.3) for the
AEY signal,

It(hv) = ~ IoAoO'~(hv)pAOJt . (5.27)

Again we have assumed the small concentration limit, i.e., O'~ pA ~ 1.

The background signal I back arises from the fluorescent signal of the sub-
strate and from the reflected and scattered X-rays according to

(5.28)

Here the reflectivity R(lJ) is zero except at the specular angle, Ids is the diffuse
scattering intensity (5.26), I~s is the elastically scattered intensity from the bulk
(5.20), and Ir is the fluorescent intensity from the bulk (5.19).
140 5. Principles, Techniques, and Instrumentation of NEXAFS

In order to understand the relative size of the various background signals in

comparison to the fluorescence signal from the adsorbate let us estimate them
assuming that all photons from the sample are detected without energy or
angular discrimination. Also, since it is necessary in practice to measure angle-
dependent NEXAFS spectra we shall carry out a worst case analysis and
consider the X-ray incidence angle that gives rise to the largest background
signal. We assume a collection angle Q = 2n and an incident photon flux
IoAo = 2 x 10 10 photons/s and consider the case of a monolayer
(pA = 10 15 atoms/cm 2) of carbon atoms on a copper surface. Below we evaluate
in tum all relevant intensities in (5.27) and (5.28) at a photon energy of
'" 300eV.
(1) It(hv): Using the X-ray absorption cross section O'~ = 10- 18 cm 2/atom
from Fig. 5.11, and wt = 3 x 10- 3 from Fig.5.2b, we obtain It = 3 x 104
photons/s for the fluorescence signal from the adsorbate.
(2) IoAoR(O): The specularly reflected background signal from the sample
is largest at grazing X-ray incidence and at the smallest X-ray incidence angle
'" 10 ° typically used in NEXAFS studies the reflectivity of the perfectly smooth
copper surface is Ro(100) ~ 10- 1 according to Fig. 5.12. Assuming aRMS
surface roughness of () = 20 A we can calculate the intensity in the reflected
beam with (5.25) to be IoAoR(100) ~ 6 x 108 photons/so
(3) Ids: Using the same parameters, we can estimate the diffuse scattering
intensity from (5.26) as Ids ~ 7 X 108 photons/so
(4) I~s: The coherently scattered intensity is obtained from (5.20). We
approximate the X-ray escape depth as l/D(hv) = {lAhv)/cos () ~ 2{lx(hv) and
with (5.2) and 0 = 90° we obtain I~s = (0'~s/30'~) X 10 10 photons/so Using the
cross sections for copper plotted in Fig. 5.11 yields I~. ~ 5 X 105 photons/so
(5) Ir: Using the same approximation for D(er) and approximating the
photon energy dependence of the absorption coefficient according to
{lx(6 c) ~ (hv/er)3 11x (hv) we obtain from (5.19) Ir ~ {wd[l + 2(hv/er)3
sin OJ} x 10 10 photons/so Around hv = 300eV only the outer shells of typical
substrate atoms are excited and fluoresce, and their fluorescence yields are very
small ('" 10- 5 ) [5.12, 13Y For copper the largest fluorescence yield ofthe outer
shells is that of the M 3 shell at 75 eV binding energy2, and with Wc = 5 x 10- 5 we
obtain the background intensity at 0 = 10 ° to be Ir ~ 2 x 104 photons/so
The above comparison predicts a signal-to-background ratio which, taken at
face value, would render fluorescence detection impractical if not unfeasible. In
particular, the specularly reflected and diffusely scattered intensities are about 4
orders of magnitude larger than the fluorescence signal from the adsorbate layer.
Fortunately, there are experimental remedies which reduce the background
signal by taking advantage of its angular and/or energy dependence.

2 Calculated fluorescence yields for the M and N shells of copper and gold are [5.67]: Copper: M 1
(123eV): 1.2xlO- s , M2 (77eV): 4.1 x 1O-S, and M3 (75eV): 5.1xl0- s . Gold: N4 (353eV): 1.5
x 10- 4 , Ns (335eV): 1.7 x 10- 4 , N6 (88eV): 3.0 x 10-5, and N7 (84eV): 3.5 x lO- s .
 5.3 Fluorescence Yield Detection 141

The conceptually simplest scheme, successfully applied in the hard X-ray

region [5.68, 69], is energy discrimination. The fluorescence radiation from the
adsorbate is emitted below the K-shell threshold, at an energy Be. For example,
for carbon Be ~ 277 eV, compared to a typical K-shell threshold of 285 eV. For
nitrogen (Be ~ 392) eV and oxygen (Be ~ 525) the fluorescence energy is also
about 8 eV below the respective K -shell thresholds of 400 eV and 533 eV. The
fluorescent radiation can therefore be isolated by means of a suitable mono-
chromator from the fluorescence radiation of the substrate atoms and from the
reflected and scattered radiation which has the same energy hv as the incident
radiation. In practice, this elegant scheme is impeded by low signal rates arising
from the restricted acceptance and low throughput of the analyzing mono-
chromator. For this reason this scheme has not yet been utilized for NEXAFS
studies of chemisorbed molecules.

5.3.4 Practical Scheme for Suppression of Background Signal

For practical purposes a useful detection scheme for fluorescence NEXAFS
studies consists of a high quantum efficiency detector which offers sufficient
energy resolution (-100-3OOeV) to eliminate unwanted fluorescence radiation
from the substrate and which is suitably positioned relative to the incident beam
and the sample in order to minimize the background signal from the substrate.
Wire proportional counters or doped semiconductor [e.g., Si(Li)] detectors
fulfill these requirements as discussed in more detail in Sect. 5.3.5.
Assuming that such detectors are available, the most important question is
how the extremely large background signals arising from the reflected and
diffusely scattered intensities can be reduced. Elimination of the reflected signal
is simply accomplished by placing the detector so that it does not see the
specularly reflected beam, e.g., underneath the sample (see Fig. 5.7). This
detector position also eliminates most of the diffusely scattered intensity. It is
important to understand this effect in more detail.
The diffuse scattering intensity Ids is peaked at the specular angle but extends
over the entire angular range. Unfortunately, very few experimental investiga-
tions of the angular dependence of the diffuse scattering intensity exist in the soft
X-ray re~ion [5.70-73]. An illustrative example at the long wavelength end,
A. = 100 A, is shown in Fig. 5.13, taken from Hogrefe'S thesis [5.70]. Here the
specularly reflected coherent intensity and the broad underlying diffuse intensity
was measured [5.70] for a 500 Athick gold film on a glass substrate which was
roughened prior to the film deposition by a polish with a 1 Jl.m diamond paste.
The experimental geometry is shown in Fig. 5.13a. The experimental spectrum,
shown as dots in Fig.5.13b, was measured in an s-polarization geometry
(4J = 0°) at an incidence angle (Jl = 10 ° from the surface. The spectrum was
normalized to the incident intensity and normalized to the Fresnel reflectivity
Ro. Therefore the reduction of the measured peak reflectivity at (J2 = 10° below
1 is entirely due to the finite surface roughness. The solid line in Fig. 5.13b is the
result of a calculation of the diffuse scattering intensity [5.70, 71] by means of a
142 5. Principles, Techniques, and Instrumentation of NEXAFS

Z <8>

0
a::
_0
500A Au/Glass
(b) ci> A = 100A Diffuse Intensity (e)
10 = 10'
CI)

c: A = 100A
~ 8,
~ -e.
;::; 10-2
1J
8, = 10' CI)

...
>
'in
.... Experiment C>
c:
c(
0
c:
$ Cl
c:
c: 10-4 .;:

~
1J 10-3
-10
..
~
(J
~ 10-6 rJl
eX 40 30 20 10 0 40 30 20 10 0
Scattering Angle 112 (deg.) Scattering Angle 112 (deg.)

Fig. 5.13. (a) Geometry for X-ray reflectivity and surface diffuse scattering measurements by
Hogrefe [5.70]. (b) Measured angular distribution of the diffuse scattering intensity from a 500 A
gold film on a glass substrate. The substrate was roughened before film deposition by polishing with
a 1 JIm diamond paste [5.70]. The data shown as dots were taken at A. = 100 A at an incidence angle
(Jl = 10° in an s-polarization geometry (</I = 0°). The experimental data have been normalized to the
incident photon flux 10 and the specular reflectivity Ro of the smooth gold surface such that the
reduction ofthe intensity at the specular angle below 1 is solely due to the finite vertical RMS surface
roughness lJ. The solid line is a fit with a scalar theory assuming lJ = 27 A, and a lateral correlation
length A = 2500 A. (e) Angular dependence of the diffuse scattering intensity as a function of (J2 and
</I. The lines represent equi-intensity profiles, normalized to the diffuse intensity at the specular angle.
The intensity variation with (J2 corresponds to the solid line in (b). Note that the scattered intensity
falls off much more rapidly with </I than with (J2' All data and theoretical results are taken from
[5.70]

so-called "scalar theory", which neglects polarization effects [S.64, 70, 71].
Because of the rather lengthy mathematical expressions for Ids in both the
"scalar theory" [S.64] or a perturbative "vector theory" [S.74] we shall here
discuss only its qualitative dependence on various parameters. We also note that
the scalar and vector theories give quantitatively different results at larger
scattering angles [S.70, 71] while both agree in their qualitative predictions. In
general Ids can be expressed as

(S.29)

where the angles have been defined in Fig. S.13.

According to (S.26) the total integrated scatter, i.e., the area under the solid
curve in Fig. S.13b, increases with increasing vertical surface roughness b at the
expense of the speculady reflected intensity. To first order, b does not affect the
 5.3 Fluorescence Yield Detection 143

angular distribution of the diffuse intensity. In contrast, the lateral correlation

length A, and A and (Jl strongly affect the angular distribution, which becomes
more peaked at the specular angle and diminished at larger scattering angles
with increasing A and (Jl and decreasing .Ie [5.70, 71, 75].
An important general result is revealed by Fig.5.13c, namely, that the
scattered intensity falls off much more rapidly in a direction perpendicular to the
plane of incidence (change of ¢, (J2 fixed), than in the plane of incidence (change
of (J2 , ¢ = 0°). The angular dependence shown by Fig. 5.13c was calculated by
means of the scalar theory [5.70, 71J but similar results are obtained with the
vector theory [5.72]. The result shown by Fig. 5.l3c is the key to eliminating
most of the diffusely scattered intensity by placing the detector out of the plane
of incidence. For a vertical sample mount, as shown in Fig. 5.7, the detector is
best mounted underneath the sample. By detecting only X-rays from the sample
within a 20° halfcone from the sample surface, centered about a vertical axis, this
detector geometry offers a reasonable solid acceptance angle (~5% of 4n sr) and
places the acceptance cone more than 70° away from the reflected beam, at any
X-ray incidence angle on the sample. Therefore, the diffusely scattered intensity
will be reduced by many orders of magnitude. Figure 5.l3c suggests that the
reduction factor will be at least 5 orders of magnitude, which would decrease the
diffuse scattering intensity to a value below the fluorescence signal from the
adsorbate.
A detector placed underneath the sample which views the sample in a
grazing geometry also reduces the coherently scattered and fluorescence back-
ground intensity. The reduction arises, similar to the case of electron yield
detection, from the angular dependence of the X-ray escape depth term
D = cosb/px in (5.19) and (5.20). At grazing emission angles (b> 70°) the
effective X-ray escape depth in the substrate and therefore I~ and I~s are greatly
reduced. At this point a comment is required about the angular dependence of
the elastically scattered intensity. For linearly polarized X-rays the scattering
cross section is not isotropic but, using the scattering geometry illustrated by
Fig. 5.14, is given by

(5.30)

Fig. 5.14. Coordinate system for a coherent X-ray

scattering process from an atom for linearly polarized X-
rays. k i is the incident wave vector along the y-axis, ks is the
scattered wave vector. The E vector lies along the x-axis. If
E lies in the scattering plane defined by k i and k" i.e., X
x = 90°, we speak ofp-polarization. The geometry", = 0° is
referred to as s-polarization
144 5. Principles, Techniques, and Instrumentation of NEXAFS

Note that the polarization factor in (5.30), 1 - sin 2 '" sin 2 X, differs from that for
unpolarized radiation, (1 + COS 2 6)/2, typically found in the X-ray literature,
where 6 is the angle between the incident and scattered beams. Integration of
(5.30) over all angles yields (5.16). For linearly polarized radiation the scattered
intensity vanishes for'" = X = 90°, i.e., when the wavevector kg of the scattered
radiation lies along the electric field vector E. For E perpendicular to the
scattering plane (s-polarization, '" = 0°) there is no angular dependence. Equa-
tion (5.30) indicates that the detector geometry dictated by the diffuse scattering
intensity is not optimal for suppression of the coherent scattering intensity,
which would favor a detector orientation perpendicular to the incident X-ray
beam, along the electric field vector. However, the suppression of the diffuse
intensity is more important, judged by its larger overall intensity.
The above general considerations are confirmed by recent measurements
carried out under conditions that resemble those of a NEXAFS study of a
carbon-containing adsorbate on a single-crystal sample [5.73]. Fischer et al.
measured the angular dependence of the scattered soft X-ray radiation from a
Pt(111) crystal at an incident photon energy of 275eV. The scattered photons
were detected with a proportional counter (Sect. 5.3.5) whose energy window
was centered around the incident photon energy. Since this energy coincides
with the carbon Ka. fluorescence energy, the experiment directly probed the
scattered X-ray background that would be present in a NEXAFS experiment of

Rotation
Axis
I (a) (b)

___
~
II

~--------/
/
/
/
/
/
/
/
/
II
Surface )n-Plane Out-of-Plane
Normal Detector

Out-of-Plane
o 25 50 75
Detector Angle of Incidence. e (deg)
Fig. [Link]. (a) Experimental arrangement used by Fischer et al. [5.73] to measure the scattered light
intensity off a polished Pt(lll) single crystal at hv = 275 eV. The (nearly) linearly polarized soft X-
rays with the electric field vector E in the horizontal plane were incident on the vertical sample at an
angle ewith respect to the surface (p-polarization). The sample could be rotated about a vertical axis
allowing measurements from grazing (e "" 0°) to normal (e = 90°) incidence angles. The scattered
light was measured with a proportional counter with a 2 x 2cm 2 detection area, located 13 em from
the sample. Two detector positions were explored, both at right angles with respect to the incident
beam direction: underneath the sample labeled "out-of-plane", and along the electric field vector
direction labeled "in-plane". (b) Measured scattered light intensity for in-plane and out-of-plane
e
detector positions [5.73]. For in-plane orientation the large peak around = 45° is due to the
specularly reflected beam. Note that at all angles the out-of-plane detection intensity is lower than
the in-plane detection intensity
 5.3 Fluorescence Yield Detection 145

a carbon-containing species on the same Pt(111) surface. The detector was

positioned such that its angular acceptance was about 10°. The experimental
geometry, pictured in Fig. 5.15a, is seen to closely reflect that of a typical
NEXAFS experiment shown in Fig. 5.7. The soft X-rays, with the (major)
electric field vector component E in the horizontal plane, are incident at an angle
e relative to the surface of the vertically oriented sample. By rotation about the
vertical axis the angle of incidence could be varied in the range 0° ~ e ~ 90° (p-
polarization geometry). The detector was positioned either underneath the
sample, perpendicular to the plane of incidence, labeled "out-of-plane", or along
the electric field vector direction, in the plane of incidence, labeled "in-plane".
The measured scattered intensity for the two detector orientations is shown
in Fig. 5.15b. Clearly the "out-of-plane" intensity is much smaller than the "in-
plane" intensity at all angles e. The large peak around e = 45° is due to the
specularly reflected X-rays which enter the detector at this angle for the "in-
plane" geometry. The angular dependence indicates that the scattered radiation
is due to diffuse surface scattering rather than coherent bulk scattering. The
results unambiguously demonstrate the advantage of "out-of-plane" detection
for X-ray fluorescence NEXAFS studies.

5.3.5 Experimental Details and Detectors

Fluorescence yield measurements are carried out using an experimental ar-
rangement similar to that shown in Fig. 5.7 with the partial electron yield
detector replaced by a suitable fluorescence yield detector. For a general review
of photon detectors in the soft-X-ray region the reader is referred to the classic
book by Samson [5.76] and the recent review by Timothy and Madden [5.55].
Two detectors, i.e., a gas proportional counter and a semiconductor Si(Li) diode,
suitable for soft X-ray fluorescence studies, are shown in Fig. 5.16. Both de-
tectors offer energy discrimination capabilities and reasonable detection efficien-
cies and have been utilized for NEXAFS [5.77-83].
The first fluorescence NEXAFS studies of chemisorbed low-Z molecules
[5.79] were carried out on the sulfur K-edge (2470eV) by use of a gas propor-
tional counter with a 127 jLm thick beryllium window of 5 cm diameter [5.79].
The detector shown in Fig. 5.16 used by Fischer et al. [5.77] and Arvanitis et al.
[5.80] for fluorescence studies at the carbon K-edge is modelled on the original
detector but utilizes two 1 jLm thick polypropylene windows of 1.75 cm diameter.
The inner window is supported by a stainless steel wire mesh of 60% transmis-
sion. The transmission of the polypropylene window as a function of photon
energy [5.84] is displayed in Fig. 5.17 and is seen to be about 83% for C K~
radiation. Other suitable windows for soft X-rays have been discussed by Henke
and co-workers [5.84, 85].
In order to improve the energy resolution, Fischer et al. [5.81, 82] have more
recently used a cylindrical detector geometry indicated in Fig. 5.18 and obtained
a carbon K~ peak whose FWHM was about 240eV or 85% of the photon
energy, close to the theoretical limit [5.85]. The detection efficiency of this
146 5. Principles, Techniques, and Instrumentation of NEXAFS

Gas Proport ional Detector

Removable Detector
Vacuum Detector Gas Head Assembly
(- 10-3 Torr) (- 200 Torr) with 0 Ring Sea l

X-rays High Voltage

Connector- Wiper
Assembly

Po lypropylene
Window
'pm Th ick
Alum inized (200A)
Polypropylene Window
(1pm) on Grid Support

SI (U ) "Quantum" Detector by Kevex Corporation

X- rays

"Quantum"/,
Window

Copper
Co ld Finger

Fig. 5.16a, b. Schematics of two energy resolving detectors for soft X-ray fluorescence detection. The
gas proportional counter (a) is the URY compatible design of Fischer et al. [5.77]. The URY
environment of the surface science chamber is decoupled from the ionization region filled with a
suitable detector gas (e.g., propane) by two 1 /lm thick circular polypropylene windows (each ~83%
transmitting for C K. radiation) of 1.75 cm diameter. The region between the two windows is
differentially pumped. The inner window is supported by a 60% transmitting stainless steel grid and
is capable of withstanding atmospheric pressure. It is aluminized (200 A) on the side facing the anode
wire in order to improve the electric field distribution. (b) The Si(Li) "Quantum" detector com-
mercially available from Kevex Corporation (San Carlos, CA, USA), which uses a special window (of
proprietary composition) to protect the high vacuum environment of the Si(Li) detector crystal. The
window offers a 10 mm 2 circular aperture and can withstand atmospheric pressure. The total
detector efficiency is shown in Fig. 5.17

detector is about 60%, as defined by the transmission of the 2 windows (83%

each) and the stainless steel grid (90%) and the unit quantum efficiency of the
detector gas. Its solid angle of acceptance is about 5 % of 4n sr. The arrangement
shown in Fig. 5.18 was designed with the goal of studying samples in the
presence of a gas, i.e., close to the reaction conditions used in real catalytic
reactions, and studies of this kind have been performed by Zaera et al. [5.82].
The efficiency of the commercially available "Quantum" Si(Li) detector
shown in Fig. 5.16 is plotted as a function of photon energy in Fig. 5.17. For
 5.3 Fluorescence Yield Detection 147

/
/'
./
---- "Quantum" detector
80
~
OK / c:
0'./ 0
'iii
/ 60 <I)

'E
L .:.... , Beryllium window (-8pm) <I)
c:
• detector <U

40 ~
~
0
"0
c:
20 ~
'--~--1pm Polypropylene
Transmission
.. '

o 1.0 2.0 3.0

Energy (keV)

Fig. 5.17. Detector efficiency of a Si(Li) detector (see Fig. 5.16) with two different windows [5.86].
The "Quantum" detector is equipped with a window made out of a proprietary material. Also shown
is the transmission through a 1 11m thick polypropylene window (mass density of 0.9 g/cm 3 ) [5.85]
used for the proportional counter shown in Fig. 5.16

comparison the efficiency of the same detector equipped with a 8/lm thick
beryllium window is also shown. The "Quantum" detector is equipped with a
permanent thin window of proprietary composition which separates the internal
detector vacuum from the sample environment. The window is opaque to visible
light and is capable of withstanding a pressure differential of 760 Torr. It
therefore allows venting of the sample chamber to atmospheric pressure without
condensing water and other contaminants onto the sensitive Si detector surface
kept at liquid nitrogen temperature. At present the active detector area is
1Omm 2 and the energy resolution is in the 80-100eV range for C, Nand 0 Ka
radiation, as illustrated by Fig. 5.19. The count rate of semiconductor detectors
is limited to about 5 x 104 cts/s.
In the future, semiconductor diodes [5.87] may also prove to be suitable
detectors for soft X-ray fluorescence studies. Although such devices are sensitive
to all incident photons above a certain threshold value (about 2-3 eV) the
quantum efficiency increases with photon energy. For example, GaAsP/Au
Schottky barrier diodes exhibit a nearly four orders of magnitude increase in
quantum efficiency between 10eV and 1000eV [5.87], thus yielding significantly
higher sensitivity to soft X-rays than to visible and UV radiation. Also, such
devices have a high absolute quantum efficiency, e.g., about 100 electrons/
photon at a photon energy of 300eV. Thus in cases where the low-energy
photon "background" from the substrate is small and energy discrimination of
substrate fluorescent peaks is unnecessary, semiconductor diodes may well
prove useful as soft X-ray fluorescence detectors. Another use of such detectors
148 5. Principles, Techniques, and Instrumentation of NEXAFS

Fluorescence Detection at Atmospheric Pressures

Sample Manipu lator

and Feed thru

./
Fluo rescence Detector . /
To Sample Prep. Chamber

Soft X - Ray Proportional Counter

Shield ing Box

O- Ring Compression Seal

2.75 inch Con f lat
Flange
Electroformed
Stainless Steel Mesh
(90% Transmitting)
1 11m
Polypropylene
Windows

Removab le
Insu lating Detector Head
End Cap ' - - -- - '
25 11m Gold Plated Tungsten
Anode Wi re
Fig. 5.18. (a) Experimental arrangement for fluorescence yield NEXAFS studies at atmospheric
pressures [5.81, 82]. The X-ray beam from the monochromator traverses two ultrathin (I000A)
supported boron and tin windows which in conjunction with a turbo molecular pump decouple the
ultra high vacuum environment of the monochromator and the storage ring from the sample
chamber. After collimation and traversing a metal grid reference monitor (10 grid) the beam is
incident on the sample which is situated in a reaction chamber. For characterization the sample can
be transferred into a conventional UHV chamber located underneath. The fluorescence radiation
from the sample is detected by a proportional counter positioned underneath the sample. This
counter [5.73], shown in more detail in (b), is of cylindrical geometry with the anode wire along its
horizontal symmetry axis in order to obtain optimum energy resolution. The radiation is detected
through two 1 JIm thick polypropylene windows (each 83% transmitting at 277 eV). The inner
window is supported on a stainless steel grid (~90% transmission). The two windows cover a
detector aperture of approximately 2 x 2 cm 2
 5.4 Comparison of Detection Techniques 149

Fig. 5.19. Pulse height spectra taken with the

(a) Nitrogen "Quantum" detector shown in Fig. 5.16 of
boron nitride and calcium carbonate bulk
samples, demonstrating the capability of
Boron Nitride
(BN )
detecting the Ka fluorescence radiation of
low-Z atoms [5 .86]. Note the energy resolu-
tion which is in the 80 eV (boron) to 100 eV
(oxygen) range

II)

;:
::l
o
()

o 200 400 600 800 1000

Photon Energy (eV)

is in combination with a filter or a monochromator, e.g., a multilayer mirror

[5.73].

5.4 Comparison of Detection Techniques

Having dealt with the details of the various detection schemes, we are faced with
the question whether there is a simple recipe for selecting a detection technique
for a given problem. In general, the technique of choice is the one yielding the
largest signal-to-noise ratio. There are, however, exceptions to this rule, namely
cases where the signal-to-background ratio becomes too small (a few percent)
and the data might be affected by normalization problems, as discussed in
Sect. 5.5. Let us therefore consider the signal-to-noise and signal-to-background
ratios for electron yield and fluorescence yield detection.
With reference to Fig. 5.20 we define the NEXAFS "signal" from the
adsorbate as I., the "background" signal from the substrate and absorption
processes in the outer adsorbate shells by I b , and the statistical noise on the total
signal 1 = Ib + 1. as In = JI.
The adsorbate signal is thus given by the edge
jump J = 1. = 1 - I b , i.e., the difference in total signal above and below the
adsorbate "edge" and in practice is estimated by the difference of the signal in
the region above the near-edge resonances, i.e., about 30eY above threshold,
150 5. Principles, Techniques, and Instrumentation of NEXAFS

Is

--f
I:
o
~
U
GI
;:;:; Ib
o __ L _________ _
'--~~~~~~~~~~~~~~~~----

Photon Energy (eV)

Fig. 5.20. Schematic NEXAFS spectrum, defining the "signal" intensity I" the "background"
intensity I b , and the "noise" In

and the signal just below the first resonance. With the above definitions we
obtain for the signal-to-background ratio

(5.31)

The signal-to-noise ratio SN is given by

I ( I )1/2 ( I )1/2
SN = I: = 1+ Ib/Is = 1+ ~/SB (5.32)

As discussed in Sect. 5.3.3, theoretical estimates of the signal-to-background

ratio for the case of fluorescence detection are quite difficult. Let us therefore
examine experimental results. Spectra for a double layer of ethylene on Cu(lOO)
recorded by different detection techniques are shown in Fig. 5.21 [5.77]. All
spectra were recorded at normal X-ray incidence on the sample with about
10 10 photons/so Fluorescence spectra were recorded with the proportional
counter shown in Fig. 5.16 using the "in-plane" geometry shown in Fig. 5.15. A
CMA electron energy analyzer was used for the AEY spectrum, with a window
of 3.2 eV width set at the KVV Auger energy of 265 eV. The partial yie14 detector
operated at - 220 V retarding voltage and was positioned in the "in-plane"
geometry. Underneath each spectrum we have listed the signal-to-background
ratio SB using the value of the signal at 320 eV as a measure of the edge jump.
Clearly, the fluorescence yield (FY) exhibits the largest SB value, about 17 times
larger than the Auger yield ratio, and about 60 times larger than the PEY ratio.
Despite this advantage of the FY, in the present case, the detection mode of
choice is the PEY mode because of its superior signal-to-noise ratio. Note that
the signal-to-noise ratio in the AEY spectrum is worse than in the fluorescence
 5.4 Comparison of Detection Techniques 151

1OL C2H";Cu(1 00). 60K Fig. 5.21. NEXAFS spectra of about two
monolayers of C 2 H 4 on Cu(l00) (exposure of
150 10 Langmuir at 60 K) recorded with different
Fluorescence Yield
detection techniques [5.77]: (a) carbon K. flu-
(a) orescence yield using the proportional counter
100 shown in Fig. 5.16 in the "in-plane" geometry
shown in Fig. 5.15a; (b) carbon KYY Auger
50 10c/s
yield, using a cylindrical mirror analyzer in the
\ geometry shown in Fig. 5.7; (c) partial electron

-
~.,
[Link]

u
~
0
0
600
Auger Electron Yield
yield using a retarding voltage of - 220 Y, and
the same "in-plane" geometry as for the fluore-
scence yield. All spectra were recorded at nor-
500 (b) mal X-ray incidence and were normalized by
division through the spectrum recorded for
400 the clean sample using the same detection
techniques, respectively. The listed So values
denote the signal-to-background ratios
300
~ 1.3 Partial Electron Yield
C
.a
~

1.2

-
L
..g.
[Link] 1.1
CD
L
L
~
u 1.0
280 290 300 310 320
Photon Energy (eV)

yield spectrum only because of shorter data acquisition time in the former. From
the count rates listed on the ordinate it is apparent that for equal data
acquisition times the AEY spectrum should, in fact, have better statistics than
the FY spectrum.
A second comparison of electron and fluorescence yield detection is shown
in Fig. 5.22, where data for half a monolayer of CO/Ni(l00) recorded with AEY
detection [5.22] are compared to data recorded with FY detection [5.82].
Experimental details are given in the figure caption. The carbon KVV Auger
yield spectra were recorded with a CMA with an energy window of 4.8 eV width
set at 263 eV and a photon flux of about 3 x 109 photons/s at a spectral
resolution of about 1 eV. The carbon K~ spectra were recorded with the
cylindrical proportional counter shown in Fig. 5.18b with a photon flux of about
1 x 1011 photons/s and a spectral resolution of about 2.5 eV. The Auger electron
spectrum and fluorescence pulse height spectrum for CO/Ni(I00) are shown in
Figs. 5.22a and c, respectively. The corresponding NEXAFS spectra are shown
in Figs. 5.22b and d. The different background is due to the normalization
procedures employed.
The question arises whether some general rules can be established about the
relative merit of the three principal detection techniques, AEY, PEY and FY.
For most NEXAFS studies an adsorbate coverage of the order of 0.1-1
152 5. Principles, Techniques, and Instrumentation of NEXAFS

(a) CO / Ni(100) CO / Ni (100)

<0 1.5 hv= 300eV hv= 290eV

~
c
Ni VB
h V~
OJ

n
~

U5~
g 1.0
!:"<t
iIl
c..> 0
0.5

O~~~~~~~~~~~~

500 1000 1500

Electron Kinetic Energy (eV) Photon Energy Detected (eV)
"0
Q)
(b) COlNi(100) :;: 6 (d) CO / Ni (100)
1.0 C K-edge <I> C K-e dge
u
C
Q> <I>
OJ 0.75 U
4
«
::J
...'"ell

i=:
> ~ 0.5 g ~",'"
> t3
~
'" u::
~ t3

:~
0'1:, 2.8 ~(')o

°
"0
<I>
.!::! "0
<0 2.4 ell
.~
E
o
2~
c;;
z E
2.0 o
z
280 290 300 310 280 290 300 310 320
Photon Energy (eV) Photon Energy (eV)
Fig. S.22a-d. Comparison of carbon KVV Auger electron yield and carbon K. fluorescence yield
detection for half a monolayer of CO chemisorbed on Ni(l00). The Auger yield measurements were
carried out at the Stanford Synchrotron Radiation Laboratory with the experimental arrangement
shown in Fig. 5.7 and use of a Grasshopper monochromator at a storage ring current of 50 rnA, a
photon flux of "" 3 x 109 photons/s, and an energy resolution of ~(hv) "" 1 eV [5.22]. The fluore-
scence yield studies were performed at the Brookhaven National Synchrotron Light Source using
the setup shown in Fig. 5.18 and an Extended Range Grasshopper monochromator at a storage ring
current of 300 rnA, a photon flux of "" 1 x 1011 photons/s, and an energy resolution of ~(hv) "" 2.5 eV
[5.82]. (a) Photoemission spectrum of the C KVV Auger peak (shown shaded) recorded at
hv = 300eV with a CMA resolution of ~E = 1.6eV. Note the large underlying background due
to secondary electrons from the Ni valence band (VB). (b) NEXAFS spectra recorded at two
X-ray incidence angles by placing the CMA detector window of width ~E = 4.8eV on the Auger
peak (Eo = 263 eV). The spectra were normalized by the TEY signal from an in situ Cu coated grid
(see Fig. 5.7). (c) Pulse height spectrum recorded with the proportional counter shown in
Fig. 5.18 at hv = 290eV. For the spectra shown the boron and tin windows shown in Fig. 5.18 were
removed from the beam. The Ni L. fluorescence peak is excited by third harmonic radiation
(870eV) which is transmitted as a small percentage of the first harmonic by the monochromator.
The separation of the C K. and Ni L. peaks demonstrates the energy resolution of the
detector which increases proportionally with the incident photon energy with a peak FWHM
of ",,85% of the primary photon energy. (d) NEXAFS spectra at the same incidence angles as
in (b) recorded by monitoring the C K. radiation, which was separated electronically from the
Ni L. peak. The spectra of the adsorbate-covered sample were normalized by division of the
spectra of the clean surface, recorded in the same geometry
 5.4 Comparison of Detection Techniques 153

monolayers is of interest. In such cases all three detection techniques exhibit a

sufficiently large signal-to-background ratio that normalization problems can
be avoided, see Sect. 5.5. The choice of detection technique is then simply
determined by optimum signal-to-noise ratio, or according to (5.32) by the size
of the adsorbate signal Is. Expressions for the adsorbate signal for electron and
fluorescence detection have been derived previously and are given by (5.3) and
(5.27), respectively. If we multiply these expressions by the respective detector
efficiencies e we obtain the general quantitative relation for the measured
adsorbate signal.

(5.33)

where p (atoms/cm Z ) is the atomic area density of the adsorbate and W the
electron or fluorescence yield of the core excitation process. We are interested in
comparing the electron and fluorescence signals for a given adsorbate and for
the same area density and incident flux. Furthermore, Sects. 5.2.4 and 5.3.5 show
that typical electron and fluorescence detectors have similar solid angles of
acceptance (Q/4n ~ 0.1) such that we can ignore detector acceptance in our
comparison. We are then left with the simple relative expression

Is ex We. (5.34)

With W = 1 for AEY and PEY, W = 0.003 for carbon K-shell excitation (Table
5.1), a CMA efficiency e = 0.05 for Auger detection, e = 0.8 for PEY detection
(Sect. 5.2.4), and e = 0.6 for FY detection (Sect. 5.3.5), we obtain We = 0.8 for
PEY, We = 0.05 for AEY, We = 0.0018 for FY detection. Hence PEY is the
technique-of-choice, with a 16 times larger count rate than AEY and a 440 times
enhancement over FY.
There are exceptions to the superiority of the PEY detection mode, however.
One such case is that of very small adsorbate coverage ( < 0.1 monolayers).
While the PEY technique will still give the largest signal-to-noise ratio, the
recorded spectrum may not be reliable due to normalization problems, i.e., the
signal-to-background ratio may be so small that structures in the background
signal may still be present after normalization (see Sect. 5.5). For such small
adsorbate coverages AEY detection or FY detection can provide a way out
because they offer larger signal-to-background ratios, as shown in Fig. 5.21,
however, higher photon flux is needed. In principle, with unlimited photon flux
the technique which offers the largest signal-to-background ratio, i.e. FY
detection, will be the technique-of-choice since the noise will not be count-rate
but shot-noise limited for all techniques. Although sufficiently high flux ( ~ 10 14
photons/s eV) will be available from advanced synchrotron radiation sources in
the 1990s to favor FY detection, it appears that radiation damage of the sample
may make use of this flux impractical.
On the other hand, FY detection is without competition for studies of
samples in gaseous environments [5.81, 82] and such studies may become very
154 5. Principles, Techniques, and Instrumentation of NEXAFS

important in the future. In this context it is important to point out that

according to (5.33) the fluorescence signal from an adsorbate layer varies with
(ixOJ!. This quantity decreases much less with atomic number Z than the
fluorescence yield OJ! alone, since the cross section increases with decreasing Z.
From Table 5.1 it is seen that the fluorescence signal from a carbon layer is only
about a factor of 4 smaller than that from a sulfur layer of equal concentration.
FY detection may therefore be valuable in the future even for a light element like
carbon.

5.5 Normalization and Background Corrections

5.5.1 General Considerations

The measured NEXAFS sample signal depends directly on the incident X-ray
intensity, and the spectra need to be corrected for variations of this intensity
with time and as a function of photon energy. Intensity variations with time may
result from instabilities of the electron beam in the storage ring. Modulations in
the X-ray intensity with photon energy are common because of energy-depen-
dent reflectivity changes of the X-ray optics in the beam line which focus (e.g., a
mirror) and diffract (i.e., a grating) the X-ray beam emitted by the storage ring
[5.45]. In addition, for monolayer concentrations of molecules on a surface,
which is our area of prime interest, the measured signal typically has a large
background component from the substrate which has to be considered in
extracting the NEXAFS signature of the chemisorbed molecule. Thus a good
understanding of the methods of normalization and background subtraction are
a prerequisite for recording reliable data and their quantitative analysis. For this
reason the following section will give a detailed discussion of the various aspects
of data normalization and background correction.
Historically, several approaches have been used to normalize the signal from
the sample. Among them are: division by the electron yield signal from a
reference grid monitor measured concurrently with the sample of interest [5.88];
division by the signal from another sample, or in the case of adsorption studies
division by the spectrum of the clean surface [5.89]; and, in studies of adsorption
on a surface, subtraction of the signal from the clean surface [5.90]. These
corrections are not equivalent. Instead, each of these approaches makes a
different type of correction which is appropriate only for particular combina-
tions of sample, energy range, and detection conditions. To understand the basis
for choosing a particular type of background correction, some of the sources of
background problems in NEXAFS spectra will be outlined.
The raw signal obtained during a NEXAFS experiment is the result of a
combination of factors, of which the signal from the species of interest may be
only a small component. Consider as an example the study of an adsorbate on a
surface, which is perhaps the most difficult case for background corrections,
 5.5 Normalization and Background Corrections 155

because the concentration, and hence the adsorbate-specific signal, is so small.

Assuming that the species of interest is the adsorbate on the surface, the raw
signal from the sample is

(5.35)
where ysam is the time- and energy-dependent yield measured from the sample;
IX-ray is the time-dependent intensity of the X-rays emitted by the storage ring;
M m is the energy-dependent transmission function of the monochromator for
the monochromatic (first harmonic) component of the light; Ms is the energy-
dependent transmission function of the monochromator for all nonmonochro-
matic components including scattered light and higher harmonics; D,::m is the
detector response to the total signal originating from the monochromatic light
D:
component; am is the detector response to the signal originating from the
nonmonochromatic light component; S::'bst is the signal characteristic of the
substrate; S~::'~ is the signal characteristic of any impurities in or on the surface of
the sample; and S~'d': is the signal characteristic of the adsorbate on the sample.
According to (5.35) the adsorbate-specific signal from the sample depends on
the following quantities which need to be optimized experimentally: the X-ray
flux from the storage ring IX-ray, the monochromator throughput for the first
harmonic M m, and the measured signal from the adsorbate D,::ms~'d':. Typically
only the last quantity is under the experimenters' direct control, and the choice
of detectors and detection techniques discussed in Sect. 5.4 can be used to
enhance this term. Closer inspection of (5.35) in the light of various detector
options reveals that it is only valid for nondiscriminating detection schemes
(total electron or photon yield). Energy selective detection schemes allow the
preferential enhancement of the signal from the adsorbate relative to that from
the substrate or impurities. This would be formally accounted for by introducing
different detector response functions D,::m for the substrate, impurity and
adsorbate signals, respectively, in (5.35). For the sake of simplicity we have not
included these various terms in (5.35), but it should be remembered for the
following discussion that by choice of a suitable detection scheme the desired
signal from the adsorbate S~'d': can be enhanced relative to the undesired
background contributions S::'bst and S~::'~.
The measured signal characteristic of the adsorbate on the surface, D,::m S:'d':,
is subject to several possible sources of interference, as is evident from (5.35). For
example, storage rings can be unstable, giving rise to an unwanted time-
dependent structure in the signal. This is contained in the term Ix_ray. The beam
line optics, especially the monochromator, used to select a specific energy from
the broad spectrum of the synchrotron radiation can also introduce structure in
a spectrum which depends upon the X-ray energy. This is particularly
troublesome near the carbon Kedge, 275-325 eV, and is contained in the term
Mm. The monochromator may also pass scattered light or higher orders oflight
with energy-dependent intensities whose effect is contained in the term Ms. The
bulk substrate can have an energy-dependent background intensity in the region
156 5. Principles. Techniques, and Instrumentation of NEXAFS

of interest which enter via the term S~~bst. This may result in absorption
structures or a sloping background underlying the spectra. Finally, impurities
on or below the surface can also interfere via the Si::'';; term. There is no general
normalization and background correction procedure that can account for all of
these problems, but fortunately most NEXAFS studies suffer mainly from one of
these background problems. Three different background corrections will now be
considered which account for problems relating to one or more of these terms.

5.5.2 Normalization by a Reference Monitor

A common normalization procedure is to divide by the electron yield signal
simultaneously obtained from a reference grid monitor as shown in Fig. 5.7. The
signal from a reference grid can be described in like manner to the signal from
the sample given in (5.35), so that the ratio of the two signals is

ysam Ix_ray[MmD::m + MsD~am] [S~~bst + Si::'';; + S~~~]

yref Ix_ray[MmD;:f + MsD~ef] [S~~~st + Si~p + S~1.J

(5.36)

where the superscript "sam" refers to the sample and the superscript "ref" refers
to the reference grid. Such a monitor provides a measure of fluctuations in the
X-ray intensity emitted by the storage ring contained in the IX_ray term which
cancels in this ratio. There are many other terms, however, which do not cancel.
For example, one problem with this approach is that the reference grid can
introduce undesired signals into the ratio because of its own NEXAFS spectrum
or that of impurities or adsorbates on the grid. This problem can be eliminated
by in situ coating the grid with a material which has no absorption edges in the
energy range of interest [5.45]. Then the two terms S~<J. and Si~p are eliminated
and S~~~st ~ const. in (5.36).
A more important problem in dividing by the signal from a reference grid
occurs if the detectors used for the sample and reference grid have significantly
different response functions. This occurs when the reference detector collects the
TEY from the grid while PEY or FY detection is used for the sample. In this case
the sensitivity of the sample and reference detectors to the monochromatic and
nonmonochromatic components of the light may differ. That is, D::m and D~am
may differ from the corresponding terms for the reference monitor. For example,
with the sample detector operated in the PEY mode the sensitivity to non-
monochromatic light, particularly higher orders, is enhanced. At the C K-edge
this leads to weaker modulations in the monochromator transmission function
in the PEY than in the TEY signal, and dividing the sample detector signal by
the reference signal leads to spurious structures which look like the inverse
monochromator transmission function. This is illustrated in Figs. 5.23a and b
for the PEY signal from a clean Mo(110) crystal and the TEY from a Au-coated
 5.5 Normalization and Background Corrections 157

CO/Mo(110) Normalization Fig.5.23. Effects of different normalization pro-

2.0 cedures applied to the partial electron yield
Division by Gold Grid
(0) (PEY) spectrum of COjMo(llO) at the C K-
1.5 edge. (a) PEY spectrum ( - 200 V retarding vol-
(b) tage) of COjMo(110) (saturation coverage at
90 K) at grazing X-ray incidence. (b) Total eIec·
,......, tron yield spectrum of a clean Au grid reference
~ monitor. (a)j(b) Ratio of the spectra in (a) and
c
:l (o)/(b) (b). Clearly, the monochromator transmission
structures at 284.7 eV and 291 eV are not pro-
...
.Q
0
perly eliminated. (c) PEY spectrum recorded
......... under the same detector conditions as (a) for the
Division by Clean Surface
~ (0) clean Mo(llO) surface. (a)j(c) Ratio of the spec-
(/)
c tra in (a) and (c). Now the monochromator
Q) 1.5 (c) structures are eliminated and a properly nor-
C
malized NEXAFS spectrum of CO on Mo(llO)
1.0 is obtained
1.5

1.0 ~
280 290 300 310 320
Photon Energy (eV)

metal grid. Thus the only time that dividing by the signal from a suitable
reference grid provides a good background correction is if the retarding voltages
of the sample and reference detector are comparable. If these conditions are
satisfied then the ratio in (S.36) becomes
ysam
'" c(ssam
yref - subst
+ ssam
imp
+ ssam)
ads' (S.37)

where C is a constant. Furthermore, if the signal from the substrate and

impurities (if present) is small and/or smoothly varying with energy then the
structures in the ratio in (S.37) are directly related to the signal characteristic of
the adsorbate on the surface.
In practice, the reference grid signal is only used for normalization if three
conditions are met: (i) the grid is properly coated to avoid spurious structures,
(ii) the same detection technique is used for the grid and sample signals, and (iii)
the signal from the adsorbate atoms is large relative to that from the other
atoms, i.e., S~d':' ~ S~~~, S~~~t. This last condition is equivalent to a large signal-
to-background ratio or edge jump ratio, which for chemisorbed molecules is
only obtainable by energy selective Auger or fluorescence detection. Of course, it
is also fulfilled for thick adsorbate layers and bulk samples, e.g., a polymer film.
An example of this type of correction is given in Fig. S.24 for a layer of
Langmuir-Blodgett cadmium arachidate chains on a Si(111) surface [S.91].
Note that the intensity instabilities of the X-ray beam, i.e., term IX-ray in (S.36),
cancel completely in the ratio.
158 5. Principles, Techniques, and Instrumentation of NEXAFS

LB Film Normalization Fig. 5.24. Normalization of the total electron

yield (TEY) spectrum of a Langmuir-Blodgett
4 film on a surface (LB) by the TEY signal from
....___ LB a clean Au grid reference monitor (grid). The
LB film was a monolayer of cadmium arachid-
3 I
I
ate [Cd(CH3(CH2)ISC02)2] on Si(lll) and
I
,-... I

X-ray Beam
the X-rays were incident at an angle of 500
~
t::
2 IlIIItabllltl•• from the surface. Because both the LB and
:l I
I
I
grid spectra were recorded in the TEY mode
...
..ci .---.. Grid and because the edge jump of the LB spectrum
~ is large compared to the monochromator
J::- transmission structures at 284.7 eV and
'iii
t:: 4 291 eV, these structures are almost completely
~ missing in the ratio curve shown at the bot-
t::
3 tom. Glitches in the LB and grid spectra
around 310eV caused by a temporary insta-
2 bility in the X-ray flux emitted by the storage
ring are also completely eliminated in the ratio
curve
280 290 300 310 320
Photon Energy (eV)

5.5.3 Division by the Clean Sample Spectrum

A second type of correction is division by the signal from a clean surface. That is,
measure the spectrum of the surface plus adsorbate, clean the surface, measure
the spectrum of the clean surface alone, and then divide by it. The ratio in this
case becomes

(5.38)

In this ratio the two detector terms and the monochromator transmission
function cancel. This method does not correct for instabilities in the X-ray
source, however, so glitches in the signal will remain. This is not a problem if the
spectra are repeatedly measured and examined for reproducibility. Assuming
there are no glitches in the data and assuming that the signal characteristic of
the clean surface and impurities (if present) are flat then (5.38) becomes
ysam
- - ""
yclcan - c(ssam
ads + B) , (5.39)

where C is a constant. The term B = S:~bst + Sr::.,; is experimentally observed as

background. An example of this type of correction is given in the bottom half of
Fig. 5.23 for CO on Mo(llO) and clean Mo(110). The PEY from the clean
 5.5 Normalization and Background Corrections 159

Mo(llO) surface is seen to provide a good reference for normalization of the

monochromator transmission structures around 284.7 eV and 291.0eV, in con-
trast to the TEY from a clean Au reference grid shown in the upper half of the
figure. Note that the shoulder at 285 eV of the n* resonance is due to a step-like
feature arising from a Fermi level step, as will be discussed in Sect. 7.4.3.
A second example, for the case of fluorescence detection, is shown in Fig. 5.25
for the C K-edge of CO on Ni(lOO). Here the FY spectrum recorded at 30°
grazing X-ray incidence for the adsorbate covered surface shown in Fig. 5.25a is
compared to that of the clean surface shown in Fig. 5.25b. Division of the two
spectra yields the spectrum shown at the bottom of Fig. 5.25, which is identical
to that shown earlier in Fig. 5.22. In this case it is important to use the clean
sample spectrum for normalization purposes because the energy-dependent
transmission of the polymer detector window needs to be corrected for. The
detector window is largely transparent at the C K~ fluorescent energy
( ~ 277 eV) but it becomes opaque at energies above the C K-edge ( > 285 eV).
Since the background of the measured signal has a significant contribution from
the coherently and diffusely scattered X-rays which have the same energy as the
incident beam, the background intensity changes as the photon energy is swept
through the window cutoff.
A variant of this method consists of dividing by the spectrum of a different
clean surface which is featureless in the energy region of interest. This type of
correction may be used if the clean surface spectrum is unavailable, e.g., if the
surface cannot be completely cleaned. An example is the study of unoccupied
surface states of a diamond single crystal by Morar et al. [5.93]. Spectra were

Fluorescence Yield Normalization

3
"0Qj CO/Ni(100)
>
ID(ij"
0 ......
c: II)

~o 2
1I)e')

oS
IDa

::::I
u:::
"0 Qj
"0> Fig. 5.25. Normalization of fluorescence yield
j!l ID
=0
CIS c:
spectra of CO on Ni(lOO) recorded with the
E
...
0
ID proportional counter shown in Fig. 5.18
011) [5.92]. All spectra were recorded at a 30°
Z~
0 incidence angle from the surface using experi-
::::I
u::: mental conditions as for Fig. 5.22. (a) Spec-
trum of the adsorbate covered sample. (b)
280 300 Spectrum of the clean sample. The ratio spec-
Photon Energy (eV) trum is denoted by (a)j(b)
160 5. Principles, Techniques, and Instrumentation of NEXAFS

recorded using an identical detection mode and geometry for the diamond
crystal and a carbon-free Si wafer in order to reliably normalize out the
monochromator transmission structures near the C K-edge. This way small
surface-related features of diamond could be identified. This normalization
method has also been used for EXAFS measurements of condensed molecules
such as cyclohexane and benzene [5.94] and of different forms of bulk carbon
such as graphite, diamond [5.95] and amorphous carbon films [5.96].

5.5.4 Subtraction of the Clean Sample Spectrum

A third type of correction involves subtracting a clean surface spectrum from
that of the sample spectrum. This type of correction differs from the other three
in that it does not correct for the transmission function of the monochromator,
instabilities in the storage ring, or detector response functions. Subtraction can
remove, however, the spectral features due to impurities in the sample or due to
substrate excitations. With subtraction the following is obtained:
ysam _ yelean

_ lelean [M Delean
X-ray m m
+ M s Delean]
s
[selean + S~lean]
subst lmp (5.40)

sam [ssam
X {l X-ray subs!
+ ssam
imp
+ ssam]
ads -
lelean [selean
X-ray subs!
+ selean]}
imp .

This correction works under the following conditions: (i) the monochromator
transmission function is reasonably flat such that [MmD:m + MsD:am] ~
[MmD~ean + MsD~lean] ~ constant, (ii) the synchrotron radiation source is
stable (verifiable by repeated measurements), and (iii) the spectra from the clean
and adsorbate covered surface are scaled in the pre-edge region such that
I"am subs! + s~am]
X-ray [ssam Imp = lelean subs! + S~lean]
X-ray [selean Imp' Then the result is directly related
to the signal characteristic of the adsorbate:
ysam _ yelean ~ C S~~': , (5.41)

where C is a constant.
This procedure is illustrated in Fig. 5.26 for molecular O 2 on Ag(llO), where
the signal from a subsurface oxygen impurity causes interference [5.90]. At the
top of this figure are shown the raw PEY spectra of the clean Ag(llO) surface
exhibiting a structure around 538 eV due to subsurface atomic oxygen and of the
O 2 covered surface. These spectra have been divided by the signal from a gold
reference grid which is flat but which provides a correction for the different
X-ray intensities of the storage ring for the two experiments. Note that the signal
from the clean surface has greater intensity than the adsorbate covered surface.
This is because the presence of the adsorbate attenuates the signal from the clean
 5.5 Normalization and Background Corrections 161

02/Ag(110) NEXAFS Fig. 5.26. Illustration of the subtraction

Background Subtraction procedure for removing artifacts in NEX-
AFS spectra caused by surface impurities
Raw
using as an example the spectrum of O 2 on
0.20
(a)
r..;..----~
Clean Ag(1I0) [5.90]. The raw PEY( -400 V re-
tarding voltage) spectra for the O 2 covered
surface (b) and the clean Ag(llO) surface (a)

-
are shown at the top. Scaling of these
"iii' 0.10 (b) spectra to the same intensity before the
edge as shown in (c) and (d) accounts for
the attenuation of the bulk silver and sub-
2.0 Scaled Spectra surface oxygen signal by the presence of
the O 2 overlayer. Subtraction of (d) from

-
(c) yields the near edge spectrum (e) where
the peak due to subsurface oxygen at
·iii 1.5

-
538 eV has been eliminated
c
CD (c)
C
1.0
(d)

0.5 Difference
(e)
0
520 530 540 550 560
Photon Energy (eV)

Ag(1lO) surface and from surface impurities. Before the spectra can be sub-
tracted they must be scaled to the same value before the edge jump, that is, in the
region before 525 eV. The bottom curve shows the result of subtracting these
two scaled spectra. The difference curve is quite well defined and isolates the
structure due to the molecular oxygen with no indication of signal from the
subsurface oxygen impurity peak at 538 eV.
It is apparent that a combination of the normalization and background
correction techniques discussed above can also be applied. For example, the
spectrum for the adsorbate-covered sample normalized by the reference grid
signal may be divided by the spectrum for the clean sample normalized to the
reference grid. In principle, this double normalization technique combines the
virtues of the individual procedures but it enhances the noise in the final
spectrum.
6. Spectra of Condensed, Chemisorbed,
and Polymeric Molecules: An Overview

Here we show how the K-shell excitation spectra of simple free molecules,
discussed in Chap. 4, evolve under the influence of extramolecular interactions
in the form of van-der-Waals or chemical bonds at surfaces, and develop a
molecular-orbital-based understanding of the systematic changes of the spectra
with increasing molecular size.

6.1 From Free to Chemisorbed Molecules

6.1.1 Influence of Extra-Molecular Interactions on K-Shell Spectra

In Chap. 4 we discussed the features characterizing the K-shell excitation
spectra of simple free molecules. Here our interest lies in whether these intra-
molecular features are sensitive to extra-molecular interactions of the molecule,
and if so, how they change. One can imagine a hierarchy of such extra-molecular
interactions in terms of their strength, ranging from van-der-Waals interactions
to strong chemical bonds. Table 6.1 summarizes the bond energies E bond of some

Table 6.1. Bond energies of molecular, chemisorption, and van-der-Waals bonds

System Bond Bond energy' Reference

[kcal/mole]b

Intra-molecular bonds
C-C ~85 6.1
C=C ~145 6.1
C""C ~190 6.1
C-H ~100 6.1
Benzene C=C 123 6.1
C-N ~70 6.1
C=N ~150 [Ref. 6.2, p. 189]
C""N ~195 6.1
N-H ~90 6.1
C-O ~85 6.1
C=O ~190 6.1
C""O ~257 6.1
O-H ~110 6.1
 6.1 From Free to Chemisorbed Molecules 163

Table 6.1. (Continued)

System Bond Bond energy· Reference

[kcal/mole]b

Solids
Graphite C=C 114· 6.1
Diamond C-C 85.4d 6.1,3
Organometallics
Mn2(CO)l0 CO-Mn 24 6.4,5
Fe (CO)s CO-Fe 28 6.4,5
Ni(CO)4 CO-Ni 35 6.4, 5
Mn(CsHsh Cp-Mn e 51 6.5
Fe(CsHsh Cp-Fee 71 6.5
Ni(CsHsh Cp-Nie 59 6.5
Ti(Cph(C 6H s Oh C6H sO-Ti 111 6.6
Chemisorbed atoms
0/Pt(111) O-Pt 55 6.7
0/Ag(110) O-Ag 41 6.8
Chemisorbed molecules
02/Pt(111)
02/Ag(110)
°2-Pt
02-Ag
8.8
11.1
6.9
6.10
CO/Ag(111) CO-Ag 6.5 6.11
CO/Cu(l11) CO-Cu 12 6.11
CO/Ni(111) CO-Ni 27 6.11
CO/Pt(111) CO-Pt 32 6.11
Physisorbed molecules
02/Graphite 02-Graphite 2.6 6.12
02/Pt (111)
Molecular solids
°2-Pt 2.8 6.13

Solid O 2 O 2-0 2 2.07 6.14

Solid C6H6 C6H 6-C6 H 6 10.4 6.15
Inert gas crystals
Solid Ne Ne-Ne 0.45 6.16
Solid Ar Ar-Ar 1.85 6.16
Solid Kr Kr-Kr 2.67 6.16
Solid Xe Xe-Xe 3.83 6.16

a Values reflect the average bond energy such that the sum of the average bond energies of the
system is equal to the total atomization energy. For solids we use the appropriate fraction of the
cohesive energy determined by the local coordination, for van-der-Waals solids we use the cohesive
energy or heat of condensation, for chemisorbed molecules the heat of adsorption.
b 1 kcal/mole = 4.184kJ/mole = 43.4meV /molecule = 504.6K x Boltzmann's constant per mol-
ecule.
• For graphite, neglecting the small van-der-Waals energy between planes, atomization involves the
equivalent of breaking 3 half-bonds per atom. Therefore the average C=C bond energy is about 2/3
of the cohesive energy (171.3 kcal/mole) [6.1].
d For diamond the atomization involves the equivalent of breaking four half-bonds per atom.

Therefore the average C-C bond energy is half of the cohesive energy (170.8kcal/mole, [6.1]. Also
see [6.3] for a recent discussion of the cohesive energy of diamond.
• Cp stands for cyc10pentadienyl (CsHs).
164 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

characteristic bonds ranging from van-der-Waals bonds in condensed gases

(E bond ~ 1 kcaljmole), molecular chemisorption bonds or molecule-metal bonds
in organometallics (E bond ~ 20kcaljmole), to strong covalent bonds within low-
Z molecules (E bond ~ l00kcaljmole).
Extra-molecular effects can therefore be studied in two steps by use of the
following systems: (i) condensed or physisorbed molecules where van-der-Waals-
type inter-molecular or molecule-surface bonds are very weak relative to
covalent intra-molecular bonds, and (ii) chemisorbed molecules or organometal-
lics where the molecule-metal bonds can range from much weaker than to
comparable to intra-molecular bond strengths. One may even consider a further
step, namely the assembly of large molecules from building blocks of well-defined
small molecules with all bond strengths being comparable. We shall consider
this later in Sects. 6.3-5. Let us start by discussing extra-molecular interactions
by means of two examples: carbon monoxide (CO) and ethylene (C 2 H 4 ). The
reason for this choice is the different ways the two molecules bond to metal
atoms and surfaces, and the fundamental importance of the two bonding
schemes for our understanding of molecule-surface bonds, in general.
The C K-shell excitation spectrum of free CO [6.17,18] is compared to those
of CO in different environments in Fig. 6.1. The spectra are arranged in the order
of increasing extra-molecular interactions from top to bottom. For Mn 2 (CO}10
[6.19] five CO molecules are chemically bonded via the C atom to each Mn

71· u·

I co Gas

~ I
I

rJ
I
I Mn2(CO)10
I
Z' I
'iii
c: I
Q)

C I
I
IP

Fig. 6.1. K-shell excitation spectra of CO in dif-

CO/Mo(110)
ferent environments: free CO [6.17, 18]
Mn2(CO)10 [6.19], and CO strongly chemisorbed
on Mo(llO) [6.20, 21]. The ionization potential
(IP) is referenced relative to the vacuum level
280 290 300 310 320 [6.19] and is lowered in the carbonyl because of
Excitation Energy (eV) relaxation effects
 6.1 From Free to Chemisorbed Molecules 165

atom. In the bottom spectrum CO is strongly bonded via the C atom to the
Mo(llO) surface [6.20, 21], with the C-O axis along the surface normal (Sect.
6.1.2). This last spectrum is the sum of two spectra recorded at grazing and
normal X-ray incidence angles (see Fig. 6.5) in order to eliminate angle-
dependent effects.
The most remarkable point is the overall similarity of the spectra, which are
all dominated by a strong n* resonance around 287.5 eV and a 0"* shape
resonance around 304eV. For chemically bonded CO in the carbonyl and on
Mo(llO), the Rydberg resonances have disappeared or, at least, are broadened
beyond recognition. The disappearance of the two-electron peak around 301 eV
in the lowest two spectra is accompanied by changes in the n* resonance
intensity for the carbonyl and the n* peak intensity and width for CO on
Mo(llO). This is the direct consequence of the chemical bond between the C and
metal atoms, and a quantitative study of these changes can provide detailed
information on the nature of the molecule-metal bond [6.19, 22]. Let us
therefore discuss the origin of the n* resonance intensity and width in more
detail.
The essence of the bonding of CO to metal atoms in carbonyls or on surfaces
is contained in the Blyholder model [6.23] and consists of interaction of the 50"
HOMO and 2n* LUMO frontier orbitals (compare Fig. 2.5) with metal orbitals.
The carbon 50" lone pair orbital forms a donor bond stabilized by backbonding
of metal dn-pn orbitals with the 2n* antibonding orbitals of the molecule.
Therefore the Is ~ 2n* transition, i.e., the n* resonance, is sensitive to the nature
of the metal-molecule backbonding interaction. With increasing bond strength
the metal dn-pn contribution to the 2n* orbital will increase and the n*
resonance intensity will decrease. This has been observed experimentally in
metal carbonyls by Riihl and Hitchcock [6.19]. In addition, the strength of the
back bond and the nature of the metal states will affect the width of the n*
resonance. Cooper et al. [6.24] have observed that in Ni(CO)4 the C K-edge n*
resonance still reveals vibrational fine structure, although somewhat different
from that observed in the free molecule (Fig. 4.1). In contrast, for strongly
chemisorbed CO the excited electron can decay into the conduction band, and
the reduced lifetime of the excited state will lead to a broadening of the
resonance according to (2.16). This is clearly seen in the COjMo(llO) spectrum
in Fig. 6.1.
The n* resonance position is rather insensitive to extra-molecular inter-
actions because bonding shifts of the Is level associated with bonding to a
transition metal are small [6.25-27] and the 1s ~ 2n* transition energies are, to
first order, not affected by relaxation shifts arising from extra-molecular screen-
ing effects. This is because the molecule remains neutral in the excitation process
and the core hole potential is self-shielded by the electron in the n* orbital. In
contrast, in X-Ray Photoemission Spectroscopy (XPS) the molecule is ionized
and the core hole is shielded by charge transfer from the metal.
For chemisorbed molecules the n* resonance lies close to the excitation
threshold, given by the Is BE relative to the Fermi level (E F ) of the substrate.
166 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

The Is excitation threshold and the n* resonance energy are similar because in
both cases the final hole state is well screened, either by metal conduction
electrons or by the excited Is electron in the n* state [6.28]. For free molecules
the n* resonance is typically not superimposed on any background originating
from other absorption channels. For chemisorbed molecules a step-like back-
ground may exist due to the fact that the excitation threshold to substrate
related states above EF falls below or close to the n* resonance energy, as
discussed in more detail in Sect. 7.4.3. Close inspection of the spectrum for CO
on Mo(llO) in Fig. 6.1 reveals a shoulder on the low energy side of the n*
resonance arising from transitions to metal conduction band states, which by
mixing with the n* molecular states have a finite projection on the molecule.
As seen in Fig. 6.1, the 0-* resonance also remains in nearly the same position.
The reason is the same as for the n* resonance, namely that the final state is
sufficiently localized to be self-screening. This is somewhat surprizing since the
excitation energy exceeds the Is ionization potential and therefore, in principle,
the molecule is ionized in the excitation process. However, as discussed in Sect.
4.2.4, the 0-* shape resonance can be thought of as an excitation to a localized
molecular orbital final state, which is neutral and self-screened, followed by
ionization through the emission of a photoelectron. Furthermore, the constancy
of the 0-* resonance position in Fig. 6.1 also implies that the C-O bond length
does not change significantly, as will be discussed in Chap. 8. This is, in fact, the
case. In most cases the bond length changes of coordinated CO relative to the
gas phase value of 1.128 A are small, with bond lengths around 1.15 A as in
typical metal carbonyl molecules [6.29, 30].
In contrast to CO, C 2 H 4 typically bonds to metal atoms and to surfaces in a
side-on geometry. This is explained by the preference of ethylene and other
unsaturated hydrocarbons to "n bond" to metal atoms [6.31]. The n bonding, in
a picture first proposed by Dewar [6.32] and later extended by Chatt and
Duncanson [6.33] is a natural consequence of the fact that the HOMO and
LUMO of ethylene are the C-C nand n* orbitals [6.34]. Similar to CO, the
bonding consists of two contributions, a donor bond involving the occupied n
orbital of the molecule and a 0- orbital of the metal and an acceptor bond
between metal dn-pn and n* antibonding orbitals of the molecule. As discussed
in more detail in Sect. 10.1, the dominance of the acceptor nature of the
molecule-surface bond can lead to significant changes in the C-C bond length
with a range from the gas phase value 1.34 A to ~ 1.5 A.
K-shell excitation spectra for C 2 H 4 in different environments are compared
in Fig. 6.2. The gas phase spectrum of ethylene [6.17, 35] is somewhat more
complicated than CO, especially the region above the IP, as discussed in Sect.
4.2.7. The 0-* resonance around 300eV is not very prominent and is preceded by
a series of peaks in the 292-29geV range. For weakly chemisorbed C 2 H 4 on
Ag(I00) [6.36] three resonances clearly dominate, the n* resonance at 285 eV,
the C-H resonance at 288eV, and the broad 0-* resonance at 300eV, indicating
that the other peaks in the gas phase spectrum are either associated with
Rydberg (see below) or multielectron transitions (i.e., peaks between 292 and
 6.1 From Free to Chemisorbed Molecules 167

Fig. 6.2. K -shell excitation spectra of eth-

ylene (C 2 H4 ) in different environments: (a)
free C 2 H4 [6.17,35], (b) C 2 H 4 weakly
chemisorbed on Ag(I00) at 60 K [6.36], (c)
C 2 H 4 chemisorbed on Cu(I00) at 60 K
[6.36,37]

280 290 300 310 320

Excitation Energy (eV)

299 eV). The 0'* resonance shift relative to the gas phase is a consequence of the
lengthening of the C-C bond. This is illustrated more dramatically in the
spectrum for ethylene on Cu(lOO) [6.36, 37] shown at the bottom of Fig. 6.2. The
C-C bond lengths are 1.34A for C 2 H 4 gas, 1.37 A for C 2 H 4 on Ag(100), and
1.44 A for Cu(100) [6.36, 37], as discussed in Sect. 8.6.3.
The effect of the chemisorption process on the n* resonance and the
Rydberg/C-H* resonances is shown in more detail in the high resolution
spectra in Fig. 6.3 [6.38, 39]. On the left, the vibrational fine structure of the n*
resonance in solid ethylene is compared to that for ethylene on Ag(lOO) and
Cu(lOO). The instrumental resolution for the spectrum in (a) was 130 meV, and
200 me V for the spectra in (b) and (c). The data are fitted with Voigt profiles
(Sect. 7.2.1) using two vibrational series, corresponding to C-C and C-H bond
vibrations, respectively. In solid C 2 H 2 , the C-C series has a vibrational separa-
tion of ~1 = 150meV, and the C-H series, corresponding to a symmetric
stretching mode, is characterized by a ~2 = 430 me V separation, as indicated in
the figure. Both series, with the same vibrational separations, are also observed
for C 2 H 2 on Ag(100). However, the line width of the components, which is
determined by the final state lifetime (2.16), is broadened from 160 me V for solid
C 2 H 2 to 280 me V. This broadening arises from the interaction of the n* orbital
'e
with the surface, introducing a finite value for in (2.16). In a physical picture,
this corresponds to a finite probability of the electron in the n* orbital to escape
168 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

C2 H 4 Fine Structure
rr" Resonance Rydberg/C-H * Resonances
4
(d)

(e)
VL

(f)

285 290
Photon Energy (eV)

Fig. 6.3. Fine structure in the K -shell excitation spectrum of ethylene. Panels (a....:) show the
vibrational fine structure in the 11:* ·resonance in (a) solid ethylene, (b) ethylene on Ag(l00), and (e)
ethylene on Cu(l00) [6.38]. The instrumental (monochromator) resolution was 130 meV for the
spectrum in (a) and ",,200meV for the spectra in (b) and (c). The shown curve fits with Voigt profiles
consist of two vibrational series for the C-C (separation ~, = 150meV) and C-H bonds (separation
~2 = 430meV), respectively. The lowest energy peak in the fit corresponds to the ground state
electronic transition. The natural widths of the ground state transitions were determined to be
160meV, 280meV and 700meV for solid C 2 H 4, C 2 H4/Ag(100), and C 2 H4/Cu(100), respectively.
The right panel emphasizes changes in the Rydberg/C-H* fine structure in the 287-290eV region
[6.39]. Here the spectra of (d) ethylene gas is compared to that of (e) solid ethylene, and (f) C 2 H 4 on
Ag(l00). The ionization potentials relative to the vacuum (Fermi) level are labeled VL (FL)

into the metal. This effect is even more pronounced for the Cu(lOO) substrate.
Now the final state lifetime has become considerably larger (700 meV) than the
C~C vibrational energy. Hence in this case the fit only included C~H vibrational
components separated by 430meV. Note that the broadening follows the
change in the C~C bond length, both being caused by increasingly stronger
bonding to the surface.
 6.1 From Free to Chemisorbed Molecules 169

The right panel in Fig. 6.3 shows ethylene spectra in the gas and solid phases,
and weakly chemisorbed on Ag(I00), over a slightly larger energy range, with
emphasis on the Rydberg/C-H* structures [6.39]. Results similar to those
shown in Fig. 6.3 for gas phase ethylene have also been obtained by Gadea et al.
[6.40]. The ionization potential is marked either "VL" when it is referred to the
vacuum level or "FL" when it is measured relative to the Fermi level. The
beautiful fine structure in the gas phase spectrum in the 287-290eV region is
significantly simplified for solid ethylene. This is the result of the inter-molecular
van-der-Waals interaction, which leads to overlap of the Rydberg orbitals and a
broadening and/or quenching of the associated transitions. The two remaining
peaks in the solid ethylene spectrum do not appear to be a simple envelope
function of the peaks in the gas phase. Instead, the two peaks probably
emphasize transitions to orbitals which have a large C-H* component. For the
solid, the ionization potential is lowered relative to the gas phase by extra-
molecular relaxation effects, and this causes the step-like background to move
down in energy and underlie the second resonance. For C 2 H 4 on Ag(I00)·only a
broad bump remains. Now the C-H* resonance lies in the continuum, which
starts at the Fermi level step (see also the fit in Fig. 6.3b) and it is therefore
lifetime broadened. There also appears to be a polarization dependent shift
( ~ 1 eV) of the peak position.

6.1.2 X-Ray Polarization and Molecular Orientation

One fundamental question in the study of interactions between molecules and
surfaces is whether the molecule will remain intact upon bonding to the surface
and, if yes, how it will orient itself. NEXAFS can answer this question with ease
as was first revealed by the K-shell spectra of CO and NO chemisorbed on
Ni(I00) [6.41, 42] reproduced in Fig. 6.4. Clearly, the spectra reveal a dramatic
angular dependence of the dominant 1t* and a* resonances. Let us turn our
attention to the origin of this angular dependence.
The principles underlying this dependence of the resonance intensities on the
orientation of the electric field vector E relative to the molecular axes are
illustrated in Fig. 6.5 for two simple cases, CO on Mo(llO) [6.20, 21] and C 2 H 4
on Ag(I00) [6.36]. We take advantage of the polarized nature of synchrotron
radiation and use the electric field vector E as a pointer. Here we assume that the
X-rays are perfectly linearly polarized and ignore the small elliptical component,
see Chap. 9. We can then rotate our sample with the molecule bonded to its
surface in the X-ray beam and thereby change the orientation of the molecule
relative to the E vector.
Figure 6.5 shows the C K-shell NEXAFS spectra recorded for the two
chemisorption systems at grazing X-ray incidence angle (E vector 20 from 0

surface normal) and normal X-ray incidence (E vector in the surface plane). For
E parallel to the surface only one peak near 287 eV, the n:* resonance, is
observed for CO on Mo(llO), while for E nearly normal to the surface this peak
is much smaller but, instead, a higher energy peak near 304 eV, the a* resonance,
is observed.
170 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

4.0 (a) CO on Ni(100) 3.0 NO on Ni(100)

C K-edge N K-edge

3.0
X-Raysh~/
By ~ 2.0
X-RaysW ~ ,
~ 7.0
.~
'c:J 2.0 c:
:J 4.0
.ci 6.0 .ci 1.0
~ ~
'0 10.0 5.0 '0 3.0
Qi Qi
:;: 9.0 :;: 6.0
4.0
liiCl 8.0 liiCl
2.0
:J 5.0
:J
« 1.4
«
c: 7.0 c:
Q)
0
.0
~
6.0 1.3 gCl
4.0 9.0
()
1.2 Z 8.0
'0 '0
Q)
.~ 1.1 Q)
.~
3.5 7.0
(ij (ij
E 5.5 1.0 E
0 0 3.0 6.0
z z
5.0 - 5.0
2.5
4.5
1T* u* 2.0 u*
4.0
280 290 300 310 400 410 420
Photon Energy (eV) Photon Energy (eV)

Fig. 6.4a, b. First NEXAFS spectra ofchemisorbed molecules [6.41]. The spectra of CO and NO on
Ni(lOO) at about half monolayer coverage were recorded by Auger electron yield detection with a
cylindrical mirror analyzer (CMA). The CMA window was set at the C (263 eV) and N (379 eV) KVV
Auger energies for CO and NO, respectively. The spectra show a dramatic polarization dependence
as a function of X-ray incidence on the sample. At normal X-ray incidence the dominant E vector
component lies in the surface plane and the n* resonance dominates, while at grazing incidence with
E close to the surface normal the u* resonance is predominantly excited. The polarization
dependence of the spectra indicates that both molecules stand up on the surface

As discussed in Sect. 3.6 the dipole selection rules governing K -shell

NEXAFS resonance intensities are quite simple: the resonance intensity associ-
ated with a specific molecular orbital final state is largest if the E vector points in
the direction of that molecular orbital, and the intensity vanishes if E is perpendicu-
lar to the direction of the orbital, i.e., lies in the nodal plane of the orbital. The
detailed expressions governing the angular dependence of resonance intensities
are given in Chap. 9.
Since the n* resonance is observed for E parallel to the surface and the 0'*
resonance for E nearly perpendicular to the surface, the CO molecule stands up
on the surface, as depicted in the figure. Furthermore, the observed spectra
clearly show peaks associated with the molecular nature of CO, such that the
molecule remains intact upon bonding to the surface. In Fig. 6.S we have shown
 6.1 From Free to Chemisorbed Molecules 171

fT'
CO/Mo(110) i
C 2 H Ag(100)

C- H'

r I

±
0
u' C-H'

~
X-Rays
H H
~
fT'
I .c~cllJ)
OC<) H W ~H
I
280
, , ,
300
I , , ,I
320 ~"
I I
280
, ,
300
,I , , ,
320
I

f2

fT'

u' 0
-E
fT'
I
~ u' , H" , ~H

I~ •
l.o.. ......

I , . .I , • ! I
C
I
,.I

••• I ! ! , I
H 0
"'C - - C"H

280 300 320 280 300 320

Photon Energy (eV) Photon Energy (eV)

Fig. 6.S. Polarization dependence of resonances. for oriented molecules, illustrated for vertically
oriented CO on Mo(110) [6.20] and lying down ethylene (C 2 H 4 ) on Ag(I00) [6.36, 43]. A transition
from the K-shell to an unoccupied molecular orbital has maximum intensity when the electric field
vector E of the linearly polarized X-ray beam points along the direction of maximum orbital
amplitude. The transition is forbidden when E lies in the nodal plane of the orbital. In general, there
is a cos 2 11 dependence of the transition intensity where II is the angle between the E vector and the
direction of maximum orbital amplitude. Note that for ethylene a resonance due to transitions to
C-H antibonding MOs is observed in addition to the main n* and a* resonances associated with the
C=C double bond. In both cases the bottom spectra were recorded at a 20° grazing X-ray incidence
angle such that E made a 20° angle with the surface normal

the NEXAFS spectra obtained by exciting the carbon atom in CO. Similar
spectra are obtained by exciting the oxygen atom in the molecule [6.20, 21].
The same concepts can be used for ethylene, as shown on the right side of
Fig. 6.5. The n* and 0'* resonances in the C 2 H 4 spectra are associated with the
C-C core of the molecule and show the opposite angular dependence to that for
CO. The n* resonance is observed for E nearly perpendicular to the surface and
the 0'* resonance for E parallel to the surface. This clearly means that the
molecule is lying down on the surface, i.e., the C-C axis is oriented parallel to the
surface. If we now consider the hydrogen atoms we expect another peak from
molecular orbitals associated with the C- H bonds. It is observed at 288.5 eV in
the spectrum recorded for E parallel to the surface, similar to the C-C 0'*
resonance. The fact that the peak is stronger for this polarization shows that the
C-H bonds lie in a plane parallel to the surface, or at least close to that plane.
Thus ethylene orients itself on a Ag(l00) surface as shown in the figure.
172 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

The two molecules discussed here are just two of tens of molecules studied by
the NEXAFS technique. Other studies, summarized in Appendix B, have not
only provided detailed information on the orientation of molecules bonded to
surfaces but also revealed changes in molecular bond lengths due to the
chemisorption bond and the transformation oflarger molecules into unique new
structures. This will be discussed later, in particular in Chap. 10.

6.2 Chemisorbed Atoms Versus Molecules

6.2.1 The NEXAFS Region

From Sect. 6.1.1, it appears that NEXAFS may be able to distinguish whether a
molecule remains intact or dissociates on the surface because of the character-
istic resonances associated with particular intra-molecular bonds, and the close
similarity between the K -shell excitation spectra of chemisorbed and free
molecules. This distinction requires that the NEXAFS spectra of chemisorbed
molecules are significantly different from those of molecular fragments, in
particular, atomic fragments. Therefore we need to understand the difference
between the NEXAFS spectra of chemisorbed atoms and molecules.
There is another reason for exploring this difference. If the NEXAFS spectra
of chemisorbed atoms exhibit detailed structures due to bonds to substrate
atoms or, in more general terms, due to scattering processes involving substrate
atoms, one would expect these structures to be present in addition to the
intramolecular resonances for chemisorbed molecules. The spectra of chemi-
sorbed molecules discussed in the previous two sections appeared to indicate
that substrate-induced structures are weak. The question arises whether this is
true in general, and if so, why.
Let us examine the above questions in detail and compare the size of intra-
and extra-molecular spectral features directly by a comparison of experimental
and calculated NEXAFS spectra of atoms and molecules. We shall limit the
following discussion to metallic substrates, which, in the context of this book,
are of most interest. It is important to point out that the discussion below
regarding the NEXAFS structures of atomic adsorbates on metal surfaces is not
generally valid for semiconductor surfaces. Because of the covalent character of
such substrates and the concomitant directionality of bonding in such systems,
pronounced molecule-like resonances may exist in the NEXAFS spectra that
arise from localized bonds between the adsorbate atom and a substrate surface
atom. Examples are the spectra of atomic CI bonded to Si and Ge surfaces
[6.44, 45].
NEXAFS spectra of atomic adsorbates on metal surfaces have been meas-
ured for a variety of surface complexes and analyzed by multiple scattering
calculations. Examples of such comparisons of experiment and theory are:
c(2 x 2) OjNi(100) [6.46], (2 x 1) OjNi(110) [6.47], p(2 x 2) and (j3 x j3)R30°
 6.2 Chemisorbed Atoms Versus Molecules 173

OjNi(111) [6.48], (2 X 1) OjCu(11O) [6.49], c(2 x 2) OjCu(100) [6.50], and

c(2 x 2) SjNi(llO) [6.51]. It is no accident that all studies listed above were of
joint experimental and theoretical nature. The reason is that our understanding
of the NEXAFS spectra of chemisorbed atoms has only been possible through
detailed calculations, in contrast to those of chemisorbed molecules, which can
be understood in a more empirical way. In all cases the theoretical method used
was that discussed in Sect. 2.9.
In order to directly compare the NEXAFS spectrum of an atomic and a
molecular adsorption system let us compare results obtained for the OjCu(100)
system with those for methoxy (CH 30-) on the same Cu(lOO) surface. In both
cases the oxygen atoms bond to the copper substrate atoms, and the 0 K-shell
spectra should therefore contain structures arising from scattering processes
involving copper substrate atoms. The methoxy spectra should furthermore
exhibit an intramolecular O-C 0'* resonance and the main question is the size of
this feature relative to the extra-molecular features.
Experimental results for the two systems [6.50, 52] are compared in Fig. 6.6a
at grazing and normal incidence angles, respectively. Clearly, the most pro-
nounced structure is a resonance around 53geV in the grazing incidence
spectrum for CH30jCu(lOO). This is the O-C 0'* resonance, which is maximized
at this incidence angle because the E vector is aligned along the O-C bond
[6.52]. The structures in all other spectra are smaller.
Although the detailed chemisorption geometries for the OjCu(lOO) [6.54]
and CH30jCu(100) [6.55] systems are still under investigation, we show in Fig.
6.6b multiple scattering calculations [6.50, 53] where we have assumed for
simplicity and lack of better knowledge that in both cases the oxygen atoms
occupy the fourfold hollow site on the unreconstructed Cu(lOO) surface and
form a c(2 x 2) overlayer. We note that in practice the c(2 x 2) structure may not
exist and the (J2 x 2J2)R 45° 0 jCu(lOO) is typically observed [6.54]. Thus the
calculations included scattering events between the adsorbate atoms in the
c(2 x 2) arrangement. For the calculations the O-Cu bond length was taken to
be 1.94 A in both cases. This is the value determined by SEXAFS for atomic
oxygen on Cu(lOO) [6.56]. The O-C bond in methoxy, approximated by a O-C
diatomic, was assumed to be perpendicular to the surface plane with a bond
length of 1.43 A, as in methanol (CH 30H). In both cases the calculations were
tested for convergence in angular momentum and cluster size.
The main finding from the data and calculations shown in Fig. 6.6 is the
dominance of the intra-molecular 0'* resonance over all other structures arising
from adsorbate-substrate scattering. Although such structures clearly exist, the
0'* resonance, when optimized by proper alignment of the E vector is about an
order of magnitude more intense. Despite this significant difference, the calcu-
lations indicate a problem in using the 0'* intensity for a quantitative determina-
tion of the molecular orientation, however. When the 0'* resonance is weak or
forbidden at a certain E vector orientation its intensity becomes comparable to
or smaller than the substrate-induced structures, leading to an ambiguity in the
assignment of the resonance intensity. This point has led to a controversy in the
174 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

Experiment

(a)

--'"
CH 30ICu( 100)

0ICu(100)

0ICu(100)

540 550 560 570

Photon Energy (eV) Energy above Threshold (eV)

Fig. 6.6a, b. Comparison of the strength of intramolecular (O-C) and extramolecular (O-Cu)
scattering resonances using atomic [O/Cu(I00)] and molecular [CH 30/Cu(I00)] chemisorption
systems as examples. (a) Experimental spectra recorded at grazing and normal X-ray incidence for
methoxy (CH 30) [6.52] and atomic oxygen [6.50] on Cu(I00). The prominent resonance at 53geV
is an intramolecular O-C u* resonance, the other structures mainly arise from scattering processes
involving copper substrate atoms. All spectra are normalized to the same edge jump (intensity near
570eV relative to the pre-edge intensity). (b) Calculated polarization-dependent NEXAFS spectra
for a chemisorbed 0 atom [6.50] and a O-C diatomic [6.53] (representing methoxy H3C-O),
chemisorbed in the fourfold hollow site on Cu(I00). In both cases the O-Cu geometry is identical
with a bond length of 1.94 A. The length of the O-C bond which is perpendicular to the surface is
taken to be 1.43 A. Only the first four Cu neighbors of the adsorbate are indicated in the icons. The
calculations included many copper shells and were completely converged with respect to all possible
neighbor atoms as discussed in the text. The threshold of the spectra is taken to be the calculated
Fermi energy of copper

determination of the orientation of methoxy on Cu(lOO) [6.52, 55]. As shown in

Fig. 6.6 there is a residual intensity at the (1* position at normal X-ray incidence
and the question is whether it is a left-over (1* or an adsorbate-substrate
structure.
The weakness of the adsorbate-substrate resonances relative to the intra-
molecular (1* resonance is somewhat surprising. After all, the chemisorption
bond to the surface should also produce adsorbate-substrate MOs with the
possibility of strong transitions to such final states. It was with the hope of
 6.2 Chemisorbed Atoms Versus Molecules 175

identifying such resonances which would yield information on the nature and
the geometry of the local bonding that Norman et al. [6.46] first calculated the
near edge structure for atomic oxygen on Ni(lOO). Unfortunately, the conclusion
drawn from these calculations is that such strong adsorbate-substrate reson-
ances cannot be identified. Rather, the NEXAFS structure results from complex
and long-range multiple scattering processes off the substrate atoms. From the
available calculations this result appears to be of quite general nature for low-Z
atoms on metal surfaces and is also confirmed by theoretical results [6.53] for
our earlier-discussed hypothetical O-C diatomic chemisorbed in the fourfold
hollow site on Cu(lOO), shown in Fig. 6.7. Clearly, for both polarization
directions the substrate-induced structures are weak when only the first neigh-
bor shells are considered in the calculations and a converged spectrum is only
obtained when shells that are as far away as 6 A are included. For example, in

Theory: Diatomic OC on Cu(100)

E ? f+
20
~~o v
---0
\ I 20 I~
0-0
Diatomic OC
Diatomic OC
Ii>
.~
c: OC/Cu(100) OC/Cu(100)
'"
~ 15 15 1 shell
1 shell
~
.~
-eco
c: 2 shells 2 shells
0
.;:; 10 10
u
OJ
Vl
'"
U
2 4 shells 4 shells

5 5

6 shells 6 shells

0 0
0 10 20 30 40 0 10 20 30 40
Energy above Threshold (eV)

Fig. 6.7. Shell by shell theoretical calculation of the 0 K-shell NEXAFS spectra for an O-C
diatomic bonded as shown in the fourfold hollow site on Cu(lOO) [6.53], with E along and
perpendicular to the O-C bond. In the structural model, the carbon atom is shown dashed, the
oxygen atom black, and the Cu atoms white. Only four of the many Cu atoms considered in the
calculation are shown, as discussed in the text. The O-C bond of 1.43 A length (as in methoxy) is
assumed to be perpendicular to the surface. The position of the 0 atom and the O-Cu bond length
are the same as for the calculations in Fig. 6.6. All spectra are plotted on the same vertical scale and
are offset from each other by a fixed amount. As for Fig. 6.6, the threshold of the spectra is taken to
be the calculated Fermi energy of copper
176 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

the calculations shown in Fig. 6.7 the first shell consisted of the 4 Cu atoms in
the surface plane at a distance of 1.94 A and a single Cu atom in the second layer
at 2.51 A, while a total of 54 Cu substrate atoms were included in the final "6
shell" calculation, the most distant ones being 4 Cu atoms at 6.64 A.
One reason why no intense resonances arising from adsorbate-metal bonds
have been identified may lie in the delocalized nature of the unfilled orbitals in
such systems. Transitions to unfilled orbitals resulting from adsorbate-metal
bonds may thus be lifetime broadened; the excited electron can rapidly decay
into the conduction band of the metal. Therefore geometry-dominated
scattering processes off higher neighbor shells within the photoelectron mean
free path (~5 A) may have comparable intensities to structures arising from
nearest neighbor chemical bonds. It would certainly be interesting to further
explore the existence of resonances due to local adsorbate-substrate bonds
using ab initio self-consistent theoretical calculations, which would be more
reliable than the previously used methods (Sect. 2.9). We shall see (Sect. 10.4)
that the first such calculation for a chemisorbed molecule (C 2 on Ag(110) [6.57])
gives evidence for the existence of such resonances.

6.2.2 The SEXAFS Region

The discussion of intra- versus extra-molecular scattering processes would be
incomplete without a look at their energy dependence, that is, a comparison of

Formate on Cu(100)

w* a*
OK-edge

+-1 Fig. 6.8. Oxygen K-edge SEXAFS spectra

of formate (HCOO) on Cu(l00) at normal
and grazing (15°) X-ray incidence, and the
blown-up SEXAFS oscillations at grazing
incidence [6.52, 58]. The formate species
was prepared from formic acid (HCOOH)
and the spectra were measured at room
temperature. The shown spectra have been
produced from the original data by divis-
ion through a smooth polynomial function
in order to emphasize the relative size of
the NEXAFS and high-energy SEXAFS
structure. It is apparent that the intra-
molecular NEXAFS resonances, labelled
1t* and u*, are considerably larger than the
SEXAFS oscillations, which originate
500 600 700 800 900 from backscattering processes involving
Photon Energy leV) the copper substrate atoms
 6.2 Chemisorbed Atoms Versus Molecules 177

the NEXAFS and higher energy SEXAFS regions. The main questions here are
whether intra-molecular scattering also dominates in the SEXAFS region, or
why and how the relative importance of intra- and extra-molecular scattering
changes with energy. Again, we shall address these questions by use of experi-
mental and theoretical results.
Unfortunately, only few SEXAFS spectra of chemisorbed molecules are
available [6.52, 58-61]. Figure 6.8 shows spectra for one of the few studied
systems, the formate anion (HCOO -) on Cu(lOO) [6.52]. Formate bonds to the
copper surface through the oxygen atoms in the bidentate configuration as
depicted in Fig. 6.8. The detailed registry relative to the substrate atoms is still
controversial [6.52, 58, 61-63]. The 0 K-edge SEXAFS spectra at normal and
grazing X-ray incidence in Fig. 6.8 exhibit the largest structures, labeled n* and
a*, near threshold with weaker periodic oscillations at higher energy.
Let us try to understand the origin of the intense near-edge and weaker high-
energy structures. This can be done by a simple model calculation as illustrated
in Fig. 6.9, where the EXAFS oscillations for two cases are shown, an oxygen
atom bonded either to a copper or to a carbon atom, similar to formate on

Energy Above Threshold (eVI

a 100 200 300 400 500
~ 1.4
(al
'" 1.2
"0
.~
C. 1.0
E
<! 0.8
Cu
'"
c
0.6
~
~
0.5
-'"
u 0.2 C

'"'" 0.0

2.0
Cu Fig. 6.9. Model calculations of O-Cu and O-C

+~~OA
1.5 EXAFS spectra using a single-backscattering EX-
AFS formalism (2.63). (a) Backscattering ampli-
...~c 1.0 tudes for Cu and C atoms as a function of excitation
ec 0.5
energy above the absorption edge. We have simply
en used the parameterized form given by Teo et al.
u.
<! 0.0 [6.64] down to threshold, although this is some-
X
w (cl
what problematic since the theory is not reliable at
"0
e 4.0 E C energies below about 60eV. Note that the energy
~1~·3A
.!!1 scale matches that used for the spectra underneath.
:J
u
<ii
u
3.0 (b) Calculated EXAFS spectrum for an O-Cu pair
with a bond length of 2.0 A and E along the inter-
2.0
nuclear axis. We have ignored the mean-free-path
1.0 and Debye-Waller-like terms in the EXAFS equa-
tion and used the backscattering amplitudes of (a)
0.0 and parameterized phase shifts as discussed in the
500 600 700 800 900 1000 text. (e) Same as (b) for an O-C pair with a bond
Photon Energy (eVI length of 1.3 A
178 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

Cu(100). The model calculations are of a very simple nature and employ the
single scattering EXAFS formalism given by (2.63), with the Debye-Waller and
electron mean free path terms omitted. For the back scattering amplitudes we
used Lorentzians of the form [6.64]

A
F(k) = 1 + B2(k _ C)2 ' (6.1)

with the parameters A = 2.122A, B = 0.6324 A andC = 0.876A -1 for carbon

and A = 0.641 A, B = 0.1842 A, and C = 7.382 A -1 for copper, taken from the
work of Teo et al. [6.64]. The back scattering amplitudes as a function of the
energy above threshold, E[eV], related to the wavevector k [A -1] by the free-
electron relation E = 3.81k2, are plotted in Fig. 6.9a. These backscattering
amplitudes were used in the calculation of the EXAFS spectra of O-Cu and
O-C pairs shown in Figs. 6.9b and c, respectively. For these calculations we also
used parameterized phaseshifts of the form
cf>(k) = X - Yk . (6.2)
The parameters X = 1.91, and Y = 0.56 for the O-C phaseshift were taken from
the empirical 0-0 phase shift derived for H 20 ice, and the O-Cu phase shift
with X = 6.17, and Y = 0.46 was derived from CU20 bulk data [6.65].
Despite the simplicity of the calculations the results are very informative.
They clearly reveal that the high-energy SEXAFS oscillations in Fig. 6.8 arise
from backscattering processes involving the higher-Z (copper) atoms of the
substrate, since the intra-molecular SEXAFS oscillations due to back scattering
events from the lighter carbon atoms are much weaker. This has also been
pointed out by Comelli and Stohr [6.66] who performed model calculations for
chemisorbed hydrocarbons on Cu(100). On the other hand, O-C scattering is
dominant at low energies, and the NEXAFS region is therefore dominated by
intra-molecular scattering events. The details of these scattering events are, of
course, not quantitatively accounted for by our crude single-scattering calcu-
lation, since we know that the 0'* and n* resonances correspond to multiple
scattering events in the detailed molecular potential. Nevertheless, the calcu-
lation yields a qualitatively correct picture.
From the spectra shown in Fig. 6.8 and the calculations in Fig. 6.9 one may
therefore draw the following conclusions. First, the NEXAFS region is domin-
ated by resonances associated with intra-molecular (multiple) scattering events
and therefore yields predominantly information on the intra-molecular struc-
ture. Second, the SEXAFS oscillations at higher energy originate predominantly
from extra-molecular (single) scattering events involving the substrate atoms and
are therefore most useful for the determination of the adsorbate-substrate
registry. Third, from extrapolation of the SEXAFS oscillations into the near-
edge region one would expect that any structures originating from extra-
molecular scattering processes are about an order of magnitude weaker than
those originating from intra-molecular scattering events. This last conclusion is
 6.3 The Building Block Approach for Large Molecules 179

in good accord with the conclusions drawn in the previous section from a direct
comparison of intra- and extra-molecular scattering in the NEXAFS region.

6.3 The Building Block Approach for Large Molecules

We shall now discuss the spectra of large molecules, which may be viewed as
small molecules joined by "extra-molecular" bonds of strength comparable to
those of the "intra-molecular" bonds. We have deliberately waited with the
discussion of the spectra of large molecules until now because it is advantageous
to use not only gas phase spectra, but also those of oriented molecules on
surfaces, prepared through condensation or adsorption from the gas phase or
through other attachment processes such as evaporation of organic solids,
Langmuir-Blodgett techniques or electrochemical deposition. The polarization
dependence of the spectra of oriented molecules greatly facilitates the assign-
ment of the various resonances for large molecules.

6.3.1 Assembly of Pseudodiatomics

As discussed above, the NEXAFS resonances of diatomic and pseudodiatomic
molecules, i.e. molecules with bonds involving a pair ofC, N, 0, or F atoms, with
additional bonds to hydrogen atoms being ignored, can be directly linked to the
n* and (]"* bonds in the molecule. In a simple picture, larger molecules can be
viewed as an assembly of such diatomic building blocks. One may therefore
envision that the NEXAFS spectra of complex molecules are simply a super-
position of those of the diatomic building blocks. The localized nature of the
NEXAFS excitations which probe the valence orbital final states near the core
of the excited atom suggests that this simple approach might work. We expect
this concept to be best applicable to large molecules which are not conjugated,
since conjugation implies strong interaction between "local" bonds resulting in
energy-split and delocalized MOs [6.67].
From Sects. 3.4 and 3.5 we can guess that the building block approach will
work best if adjacent "localized" bonds have characteristic anti bonding orbitals
of a given symmetry that are well separated in energy, such that first-order
bond-bond interactions within the n* or (]"* manifolds are absent and second-
order interactions are weak (Fig. 3.5). In a picture where hyperconjugation effects
[6.68] are viewed as a second-order perturbation caused by the interaction of a
localized single bond with an adjacent double or triple bond we would therefore
expect the building block picture to also pertain to hyperconjugated molecules.
Below we present results for some molecules which satisfy the above criteria.

6.3.2 Experimental Examples: Free, Adsorbed, and Polymeric Molecules

A beautiful example of the building block picture is provided by the K -Shell
excitation spectrum of acetonitrile (CH 3 CN) [6.69]. If, for the moment, we
180 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

Fig. 6.10a, b. Demonstration of the

a,*
c-c building block principle of K-shell
excitation spectra. (a) Gas-phase
ISEELS spectra of ethane (C 2 H 6 )
--._ _~ Gas [6.71,72] hydrogen cyanide (HCN)
[6.70] and acetonitrile (CH 3 CN)
[6.69]. The spectrum of acetonitrile
can be understood as a superposi-
tion of those of the other two mole-
cules. (b) Comparison of K-shell ex-
citation spectra of acetonitrile as a
Condensed free molecule, condensed as a thick
multilayer and chemisorbed as a
monolayer on Ag(llO). The insensi-
tivity of the spectra to the phase of
the molecule indicates that the
Chemisorbed
on Ag(110) main resonances arise from trans-
itions between states that are
strongly localized on the molecule

280 290 300 310 290 300 310 320

Photon Energy CeV)

ignore the H atoms, the C-C:=N skeleton of the molecule consists of the
diatomic C-C and C:=N building blocks. Therefore we expect the H3C-C:=N
spectrum to look like the sum of the hydrogen cyanide (HC:=N) [6.70] and
ethane (H3C-CH3) [6.71] spectra. Figure 6.10 shows this is indeed the case, and
the acetonitrile spectrum contains the C-C 0-* resonance of ethane and the C:=N
n* and 0-* resonances of HCN. There is also an indication of C-H and/or
Rydberg resonances in the CH 3CN spectrum in the region 288-292 eV, similar
to those in HCN and C 2 H 6 .
Figure 6.10 also shows that the spectrum of the free acetonitrile molecule is
almost identical to that of a condensed acetonitrile multilayer and that of
acetonitrile chemisorbed on Ag(llO). This is in good accord with our earlier
results for CO and C 2 H 4 (Figs. 6.1 and 6.2) and demonstrates that the K-shell
excitation spectra of larger molecules are also nearly unaffected by extra-
molecular interactions, provided the internal structure of the molecule is pre-
served. In our example, both the weak inter-molecular van der Waals inter-
actions in the solid and the weak chemisorption bond to the Ag(llO) surface do
not change the intramolecular structure. Also, it appears that for larger mole-
cules some of the detailed Rydberg/C-H structures that are present in the
spectra of the building blocks simplify or vanish.
Another example of the building block picture is shown in Fig. 6.11.
Here a series of complex alcohols containing C-H, C-O, and C-C single,
double and/or triple bonds, namely, methanol (CH30H), n-propanol,
(CH 3-CH 2 -CH 2 0H), allyl alcohol (CH 2 =CH-CH 2 0H), and propargyl alco-
hol (CH:=C-CH 2 0H), were condensed on a cold substrate at 120 K so that ice
 6.3 The Building Block Approach for Large Molecules 181

Condensed Alcohols Fig. 6.11. Carbon K-edge NEXAFS spectra of

condensed propargyl alcohol (HC=C-CH 20H),
allyl alcohol (H 2C=CH-CH 20H), n-propanol
n;.c C-H• (H3C-CH2-CH20H), and methanol (CH 30H)
at an X-ray incidence angle of 20° [6.74]. These
•
ac-e.c-o spectra show that the NEXAFS spectra of the
complex alcohols are simply a combination of
features due to the individual bonds comprising
the molecules

...
.a
c
"-'

280 290 300 310 320

Photon Energy (eV)

layers were formed. We note that similar results to those shown are obtained for
the free molecules [6.73] and weakly chemisorbed molecules [6.74].
For the simplest molecule, methanol, characteristic resonances of the alcohol
group are observed, i.e., two C-H*/Rydberg resonances around 28geV and a
c-o a* resonance at 293eV. 1 As shown in Fig. 4.5, a similar spectrum for
methanol is also observed in the gas phase [6.73, 75]. The NRXAFS features
associated with the alcohol group are expected to be relatively invariant since
this group varies little structurally from molecule to molecule. In accordance, all
of the alcohols exhibit the NEXAFS features of this group. The spectra of the
complex alcohols exhibit additional resonances associated with the other local
bonds in the molecule. All of the complex alcohols have a C-C bond, and
therefore a peak in the region of 292 eV is expected for the C-C a* resonance, by
comparison to the NEXAFS spectrum of gaseous ethane. Such a peak is present
in the case of the complex alcohols, but it overlaps with the c-o a* resonance
and is not distinctly resolved. Therefore the spectrum of propanol looks similar
to that of methanol with an increase of total absorption intensity above 291 eV.
Also, a change in the C-H* resonance is observed. The resonance is less
pronounced in propanol and exhibits a shoulder at lower energy around
287.5 eV. This feature arises from the additional C-CH3 and C-CH2 end groups
in propanol which give C-H* resonances chemically shifted from the O-CH3 or
O-CH2 groups according to Fig. 4.17.

1 The assignment of the resonances at 28geV and 293 eV differs from that originally given in [6.75]
for methanol. For the correct assignment see [6.73,74].
182 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

As expected, the spectrum of allyl alcohol has a sharp C=C n* resonance at

284.4eV and a C=C 0"* resonance at 300eV like the 284.8eV and 301 eV peaks
in the NEXAFS of ethylene shown in Fig. 4.12 and Fig. 6.2. Finally, the
NEXAFS spectrum of propargyl alcohol has a sharp C=C n* resonance at
285.7 eV and a broad C=C 0"* resonance at 310 eV, similar to the spectrum of
gaseous acetylene shown in Fig. 4.12. From the above studies it appears that the
NEXAFS spectra of these polyfunctional molecules can be described as a
superposition of the features of the individual diatomic building blocks compris-
ing the molecule.
An example demonstrating the assembly of diatomic C-C building blocks to
a larger functional group and the further assembly of this group to a polymer is
shown in Fig. 6.12. Here spectra of gaseous 2-butene, CH 3 -CH=CH-CH 3
[6.76], are compared to that of two polybutadiene polymers,
[-CH 2 -CH=CH-CH 2 - ]n' with different molecular weights [6.77]. The 2-
butene spectrum exhibits all resonances expected from a superposition of those
of ethane (C-C 0"* and C-H resonance; see Fig. 4.12) and ethylene (C=C 0"* and
n* and C-H resonance; see Fig. 4.12 or Fig 6.2), in accordance with the building
block principle. In addition, the spectra of 2-butene and polybutadiene, which
consists of 2-butene building blocks, are very similar. The difference between the
two polymer spectra in Fig. 6.12 is caused by a difference in molecular weight,
which affects the concentration of C=C n bonds. The lower spectrum is of a

Butene and Polymers

'c
~

~
~ (a)
:e
~
~
Fig. 6.12. K-shell excitation spectra of butene and
'in
c: polybutadiene. (a) IS EELS spectrum of gaseous
l!l butene [6.76], (b) NEXAFS spectrum of a low mo-
c:
(b) lecular weight polybutadiene polymer, and (c)
NEXAFS spectrum of a high molecular weight
polybutadiene polymer [6.77]. The spectra are all
1"emarkably similar since the molecules all contain
the same types of bonds. For the two polymers, the
(e) concentration of C=C double bonds is lower in the
m<n
high molecular weight sample (c), which manifests
280 290 300 310 320 itself in the NEXAFS spectrum as smaller C=C n*
Excitation Energy (eV) and 0'* resonances
 6.3 The Building Block Approach for Large Molecules 183

sample with higher molecular weight and clearly has fewer C=C n* bonds. This
is reflected in the spectra by smaller intensities for the C=C n* and (1*
resonances compared to the middle spectrum, which is of a polymer of lower
molecular weight.
The results shown for acetonitrile, the complex alcohols and the hydro-
carbons in Figs. 6.10-12 are also examples of the general rule that for larger
molecules Rydberg and multielectron resonances are less pronounced than for
the smaller molecular building blocks.

6.3.3 Theoretical Foundation of the Building Block Picture

The building block picture predicts that the K-shell spectrum of a selectively
excited atom in a complex molecule should only exhibit resonances associated
with n or (1 bonds of that atom. Since experimental spectra average over all
atoms of a given kind in a complex molecule it is difficult to test this prediction
in practice. Theory provides a way out. Since calculations can be performed with
the core hole localized on a selected atom, one can calculate separate spectra for
the different atoms in a molecule.
An example of such a calculation for propene is shown in Fig. 6.13 [6.78].
Using the Xcx-MS method we have calculated the three displayed spectra
corresponding to the core hole being localized on one of the three inequivalent
carbon atoms of the molecule. For each spectrum, the excited atom is indicated
by an asterisk in the structural formula.
As expected from the building block picture, a n* resonance around 285 eV
and a (1* resonance around 297 eV (dotted shading) corresponding to the C=C
bond are observed when either of the two carbon atoms involved in the double
bond is excited. For the Sp3 hybridized third carbon atom, the n* resonance is
absent, and only a (1* resonance around 291.5 eV (hatching) corresponding to a
C-C single bond is observed. The central carbon atom exhibits both a C-C and
a C=C (1* resonance, since it is involved in carbon-carbon single and double
bonds.
More theoretical results obtained with the Xcx-MS method are shown in Fig.
6.14 for a series of hydrocarbons containing single, double and triple
carbon--carbon bonds. The molecules have been selected (see also Figs. 8.13 and
8.21) such that adjacent carbon--carbon bonds, if present, are different. This
insures the absence of strong first-order bond-bond interactions, which are dealt
with in the next section. The spectra shown in Fig. 6.14 represent an average
over all atoms in a given molecule. A n* resonance is observed only for the
molecules containing double or triple carbon--carbon bonds, with the C=C n*
resonance being lower in energy than the C=C n* resonance by about 1.5 eV, in
good accord with the 1.2 eV difference found experimentally between ethylene
(284.7 eV) and acetylene (285.9 eV). At higher energy three characteristic
carbon--carbon (1* resonances are found, a C-C resonance around 291 eV
indicated by hatching, a C=C resonance around 296eV highlighted by dotted
shading, and a C=C resonance near 308eV shown cross-hatched. Comparison
184 6. Spectra of Condensed, Chemisorbed, a,nd Polymeric Molecules: An Overview

Propene Theory Fig. 6.13. K-shell excitation spectra for pro-

pene (H3C- CH=CH2)' calculated with the
Xcx-MS technique, assuming the excitation is
localized on different carbon atoms [6.78] as
indicated by an asterisk. For the C atoms
involved in a double bond, a characteristic 17*
resonance around 297 e V (dotted shading) is
observed, while a 17* resonance around
291.5 e V (hatched shading) is observed for
those atoms involved in a single bond. For the
central C atom, both resonances are observed,
as expected from the building block picture

320
Exc itation Energy leV)

Fig. 6.14. K-shell excitation spectra calculated

by means of the Xcx-MS technique for various
hydrocarbons, consisting either of a single C-C,
C=C or C=C bond or two different adjacent
bonds. Spectra are shown for, from top to bot-
tom, ethylene (H 2C -CH2)' propene (H3C - CH
=CH 2), ethane (H 3C-CH 3), methylacetylene
U·c ! C (H 3C-C=CH), and acetylene (HC=CH) [6.78].
I H3C-C~ CH

r
Resonances associated with 17* double bonds
are indicated by a dotted shading, those with
..
: ' single bonds are horizontally hatched, and those
with triple bonds are cross-hatched. The ob-
served 17* resonances follow the building block
picture. The small glitches which occur in some
H~CH
spectra at the positions of the IPs are artifacts
arising from joining the bound state and con-
tinuum regions of the spectra. Note that the
310 320 molecules with three carbon atoms have more
Excitation Energy (eV) than one IP
 6.4 Limitations of the Building Block Picture 185

of the structural formulas of the molecules with their spectra clearly reveals
the building block principle.
The building block picture is theoretically founded in the second-order-in-
teraction concept discussed in Sects. 3.4 and 3.5. This concept applies when
the characteristic bond "energies" (i.e. resonance positions) associated with
the building blocks are sufficiently different (;:0; 5 eV) such that bond-bond
interactions (-1 eV) merely cause small energy perturbations as illustrated in
Fig. 3.5.

6.4 Limitations of the Building Block Picture

6.4.1 Effects of Conjugation
In chemistry textbooks the term "conjugation" is typically used synonymously
with the term "delocalization" [6.2, 67] to describe the formation of extended n
orbitals covering a number of atoms. Examples of conjugated molecules are
butadiene (H 2 C=CH-CH=CH 2 ) with two interacting double bonds or the
aromatic molecule benzene, where conjugation causes all C-C bonds to be
equivalent (Sect. 3.5.2).
We shall here use the term "conjugation" in a more general sense. Following
Dewar and Dougherty [6.79, 80] we shall refer to conjugated systems as those
where first-order bond-bond interactions (Sect. 3.4.1) are significant. Thus we
shall consider n as well as u conjugated molecules, the simplest examples being
butadiene and propane as illustrated in Fig. 3.9. Such a treatment is suitable for
our discussion of K-shell excitation spectra because the energy splitting of u*
resonances caused by u* bond-bond interactions is of similar size to or larger
than those of n* resonances found in conventionaln-conjugated molecules. We
shall first discuss conjugation effects in n-systems, then in u-systems, and finally
in aromatic rings, where both n* and u* bond-bond interactions are important.

6.4.2 n* Bond-Bond Interactions

The formation of n bonds through interactions between "localized" p-orbitals
has long been studied in detail using Hiickel or Pariser-Parr-Pople model
Hamiltonians [6.81]. On the experimental side the splitting of the occupied
orbitals has been investigated with photoemission spectroscopy [6.82] and that
of the unoccupied orbitals with electron transmission spectroscopy [6.83, 84]
and inverse photoemission spectroscopy [6.85, 86]. We present three examples
of interactions in the n* system of molecules and their effect on the n*
resonances observed in K -shell spectra.
Butadiene (H 2 C=CH-CH=CH 2 ) is often used as an example to illustrate the
effects of n conjugation, in general [6.81], and in terms of its effect on the energy
positions of the occupied [6.82] and unoccupied [6.84] n orbitals, in particular.
We shall also use this molecule as an example here, and Fig. 6.15 shows its K-
shell excitation spectra in the gas phase [6.76], condensed as a solid multilayer,
186 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

Butadiene Fig. 6.15. Splitting of the n* resonance in

H
butadiene (H 2 C=CH-CH=CH 2 ) due to
"1 I H conjugation, illustrated by the ISEELS
,,'12 a~_c o*c=c
H-c"'c_6
I "'C-H
spectrum of the free molecule [6.17], the
H I NEXAFS spectrum of a multilayer on
H
Ag(llO), and the polarization-dependent
Gas
NEXAFS spectra of a sub-monolayer on
Ag(llO) [6.87]. The positions of the two
"E n* resonances are marked by two solid
'""
+-
Multilayer/Ag(110) vertical lines and the resonances are clearly
~
observed in all spectra. Note that the po-
~
:e
~
larization dependence of the monolayer
spectrum allows the unambiguous distinc-
~
.;;; tion of the n* resonances from the C-H
c:
j!!
c:
and C-C u* resonances. From the mono-
Monolayer/Ag( 110) layer spectra butadiene is seen to lie down

1v-.... in a n-bonded geometry on the silver sur-

face.

~I
280 290 300 310 320
Excitation Energy (eV)

and weakly chemisorbed on Ag(llO) [6.87]. From the building

block picture we expect to see a spectrum similar to that of butene
(H 3 C-CH=CH-CH 3 ) consisting of a n*, a C-H*, and two u* resonances,
which, in fact, are observed. Closer inspection of Fig. 6.15, however, reveals that
there are two n* resonances at about 284.5 eV and 287.5 eV, respectively, as
indicated by the labels n! and n! in the figure. The existence of the second n!
resonance is unambiguously established by the polarization-dependent mono-
layer spectra. At grazing X-ray incidence the two n* resonances dominate, while
they nearly vanish at normal X-ray incidence. In contrast, the polarization
dependence is reversed for the C-H* and u* resonances which clearly shows
that the plane of the molecule is parallel to the Ag(110) surface. This is thus a
beautiful example of where the orientation of a molecule on a surface and the
symmetry selection rules can be used to assign the origin of a new spectral
feature.
The splitting of the n system in butadiene into two antibonding n* orbitals
is, of course, predicted by theory as a consequence of conjugation, as discussed
in Sects. 3.4 and 3.5. It is easily understood with reference to Figs. 3.6 and 3.9 as
arising from bond-bond interactions between the two C=C double bonds. In a
perturbation treatment both "localized" double bonds have identical n* anti-
bonding orbitals and the splitting is caused by the first order interaction
between the two energetically degenerate orbitals. The observed splitting of
3.0eV is in reasonable agreement with the 3.4eV value, calculated by Yokoyama
et al. [6.88]. The energy positions and relative intensities of the 11:* resonances
 6.4 Limitations of the Building Block Picture 187

are strongly influenced by the presence of the core hole, as discussed in more
detail in Sect. 6.4.6.
A second example of n conjugation is shown in Fig. 6.16, where the K-shell
excitation spectra of free methylacetylene (H3C-C=CH) [6.17] is compared to
that of condensed 2,4-hexadiyne (H3C-C=C-C=C-CH3) [6.89]. For the pre-
sent discussion it is unimportant that one of the spectra corresponds to the gas
and one to the solid phase, since the spectral features are independent of the
phase of the molecules. From the structural formulas it is apparent that 2,4-
hexadiyne can be constructed by linking two methylacetylene molecules, and the
building block picture would therefore predict almost identical spectra for the
two molecules. While the methylacetylene spectrum exhibits the various reson-
ances expected from the building block picture, there is a pronounced additional
resonance near 290eV in the 2,4-hexadiyne spectrum. As in butadiene this
resonance is due to a second n* antibonding orbital, resulting from the inter-
action of the two triple bonds in the molecule as discussed in Sect. 3.4. This
assignment is supported by the polarization dependence of spectra for 2,4-
hexadiyne monolayers on Ag(110) [6.89]. It is interesting to point out that 2,4-
hexadiyne, in addition to the outermost C-C single bond of 1.46 A length and
the 1.21 A long C=C triple bond, has a central C-C bond which through
conjugation in shortened to 1.38 A. In the figure we have assigned a resonance
near 299 eV, labeled uj, to correspond to this bond as predicted by the building
block picture.

TT'
Methylacetylene Gas
H,
H-C-C=C-H
H/
Fig. 6.16. Splitting of the n· resonance in
hexadiyne, revealed by comparison of the
gas phase IS EELS spectrum of methylace-
I tylene [6.17, 90] with the NEXAFS spec-
I
I
I
trum of a condensed multilayer of hexa-
I diyne [6.89]. In contrast to methylacetyl-
I
I ene two n· resonances, labeled nt and n!,
I
are observed for hexadiyne, originating
2,4-Hexadi'yne Solid
from interaction of the two triple bonds. In
H, /H both molecules two C-C u· resonances are
H-C-C=C-C=C-C-H observed, corresponding to the single (ut)
H/ I· 'H
I I and triple (un bonds, with bond lengths of
I
1.46 A and 1.21 A. A third resonance in
I
I I

hexadiyne, labeled u~, appears to arise

from the central C-C bond which is signi-
ficantly shortened by conjugation to 1.38 A
280 290 300 310 320 from the nominal single bond value of
Excitation Energy (eV) 1.53 AO
188 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

Fig. 6.17a, b. Effects of conjugation on 71:* reson-

(a) ances in propiolic acid [6.74]. (a) Comparison of
1T* .
c=c ! NEXAFS spectra for propargyl alcohol

~
: 1T~=o (HC=C-CH 20H), propanoic acid
j : ......•....•.... (H3C-CH2-COOH), and propiolic acid
! , HLc=c":::'CH20H
A I 1 ....................... (HC=C-COOH), all condensed on Si(111) 7 x 7.
The top two spectra show the 71:* resonances of
,
: I
,: I
molecules with isolated 71:* bonds which are not
conjugated. The 71:* bonds of propiolic acid (bot-
tom) are conjugated, however, which is manifest as
a splitting of the C=C 71:* resonance into two
peaks. (b) Positions of the unfilled 71:* MOs, cor-
responding to the various 71:* resonances, relative
to the vacuum level. Note that the energies are
negative, indicating a positon below the vacuum
level. The energy positions are obtained by sub-
tracting the respective IPs from the NEXAFS
resonance positions
284 286 288 290 292
Photon Energy (eV)

--"
(b)
o
A ....... - -5 :>
, ~
......

-
>- ~

.--
~
Q)
c:
\::. : : . . . C -6 ,gE
W
....... ::..
B >-
E ~
.n
Q)

-7

Finally, we shall discuss an example of a second order bond-bond inter-

action effect. It is observed in propiolic acid (HC=C-C0 2 H), where the inter-
action between the n system of the C=C triple bond with that of a C=O double
bond in the carboxyl group is found to lift the degeneracy of the two orthogonal
C=C n bonds [6.74]. As shown in Fig. 6.17a, the threshold region in the C K-
shell spectra of propargyl alcohol (HC=C-CH 2 0H) and propanoic acid
(H 3 C-CH 2-C0 2 H), condensed as a multilayer on Si(111), exhibit the expected
n* resonances associated with the C=C and c=o bonds, respectively, in
analogy with the 285.9 eV n* resonance in free acetylene (Fig. 4.12) and the
288.6eV (288.2 eV) n* resonance in condensed (gas phase) formic acid [6.74, 91].
In these molecules the n bonds are isolated and hence unperturbed by any
bond-bond interaction. In the propiolic acid spectrum, however, there is
interaction between the C=C n bond and the C=O n bond as indicated by the
dotted and dashed ovals in the structural formulas in the figure. This conjuga-
tion splits the C=C n resonance into two components at 284.8 and 286eV.
The resulting energy level diagram for the n* orbitals relative to the vacuum
level is shown in Fig. 6.17b. Here we have subtracted the respective C Is IPs
from the corresponding n* resonance positions [6.74]. From this diagram it is
 6.4 Limitations of the Building Block Picture 189

apparent that the C=C n* orbital associated with peak "c" is more strongly
affected by conjugation than the orbital associated with peak "D". The diagram
also makes it clear that in our present example the bond- bond interaction is of
second order, unlike butadiene and hexadiyne discussed above, since the "local-
ized" unperturbed orbitals associated with peaks "A" and "B" are non-
degenerate.
The details of the interaction between the two n* systems are revealed more
clearly by the angular dependence of the n* resonances is condensed propiolic
acid (Fig. 6.18a). The polarization dependence arises from preferential stacking
of propiolic acid dimers in the multilayer relative to the Si(lll) substrate as
illustrated in Fig. 6.18b. At normal X-ray incidence (() = 90°) where the E vector
lies in the plane of the surface, the component of the C=C n* orbital at 286.0eV
(horizontal hatching) is favored, indicating that it lies in or near the plane of the
surface, as indicated by the horizontally hatched n* orbital in Fig. 6.18b. At
grazing X-ray incidence (() = 20°) E lies near the surface normal, and the C=O
n* orbital (black) is favored as well as the component of the C=C n* orbital at
284eV (vertical hatching). This implies that the lobes ofthese two n* orbitals are
oriented near the surface normal as indicated in Fig. 6.18b. Therefore the
interaction between the parallel n* orbitals shown black and vertically hatched
in Fig. 6.18b removes the degeneracy of the two C=C n* bonds. Since these two
orbitals correspond to peaks "E" and "c" in Fig. 6.17 the orbital diagram in Fig.
6.17b directly confirms this interaction. As a result, the resonance due to the
C- C n* orbital which is perpendicular to the C=O n* orbital is almost unshifted

PropioliC Ac id NEXAFS

Fig. [Link], b. Assignment of 11* resonances and ori-

entation of propiolic acid condensed on Si(111) (7
x 7) [6.74]. (a) 11* peaks in the carbon K edge of
propiolic acid at X-ray incidence angles of 90° and
20°. The C=O 11* peak at 288.9 eV (solid shading)
has the same polarization dependence as the C=C
11* peak at 284.8 eV (vertical hatching) indicating
that the lobes of these orbitals are parallel. The
C=C 11* peak at 286.0 eV (horizontal hatching) has
the opposite polarization dependence, showing that
the corresponding 11* orbital is perpendicular to the
other two. (b) Schematic of the orientation of pro-
piolic acid dimers on the Si(lll) (7 x 7) surface and
284 286 288 290 of the 11* orbitals corresponding to the resonances
Photon Energy (eV) in (a). For simplicity, only half of the 11* orbitals are
B shown since horizontal and vertical 11* orbitals
exist, of course, on both molecules in the dimer.
From the incomplete polarization dependence of
(b) H -C-C-C
,
"
0
,", 6 ,
" 0,
.I bhl
hi'" ,
C-C - C - h',
the spectra in (a) it can be derived that the dimer
planes are tilted from the surface plane, on average,
by 37°. The tilting is due primarily to a rotation
about axis A [6.74]
190 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

in energy (286 eV) from the n* resonance in acetylene, while that arising from the
C-C n* orbital parallel to the c=o n* orbital is shifted to lower energy by
1.2eV.

6.4.3 a* Bond-Bond Interactions

Because unoccupied 0"* orbitals are typically higher in energy and therefore
more delocalized than n* orbitals they are more difficult to observe by tech-
niques such as electron transmission spectroscopy [6.84] and inverse photo-
emission. Their overlap with the continuum also makes them more difficult to
investigate theoretically, and therefore less detailed experimental and theoretical
information is available regarding their splitting due to bond-bond interactions.
K -shell excitation spectra, on the other hand, readily reveal the effects of
interactions between adjacent 0"* bonds, and below we shall give some examples.
We shall first discuss linear and cyclic hydrocarbons and then some molecules
with multiple unsaturated bonds between carbon and oxygen atoms.
At first sight the spectra of saturated hydrocarbon chains, or paraffins,
shown in Fig. 6.19, appear to be another example of the building block principle.

Saturated Chains Saturated Rings

A B
I

IP

280 290 300 310 320 280 290 300 310 320
Electron Energy Loss (eV)
Fig.6.19. ISEELS spectra of various saturated hydrocarbons in the form of (a) chains [6.72] and (b)
rings [6.92]. All spectra in (a) are dominated by two resonances "A" and "8" arising from transitions
to C-H and C-C antibonding molecular orbitals, respectively. The weaker structure "c" at higher
energy can also be attributed to transitions to C-C antibonding orbitals with the energy splitting
between resonances "8" and "C" caused by bond-bond interactions within the u* C-C system. For
the rings the position and separation of the higher energy resonances does not follow the same
simple pattern as for the chains due to effects of bond strain
 6.4 Limitations of the Building Block Picture 191

The spectra are dominated by two resonances, labelled "A" and "B", which we
have already identified with C-H/Rydberg and C-C a* orbitals in the discus-
sion of the ethane (C 2H 6 ) spectrum in Sect. 4.2.7. A more detailed investigation,
however, reveals that the story is more complicated. The first evidence against
the building block picture comes from the spectra of saturated hydrocarbon
rings, also shown in Fig. 6.19. It is apparent that only the first resonance "A" is
common to the ring and chain spectra. At higher energy more than one
resonance is observed in the ring spectra and the shape and position of these
resonances vary. Only for the largest ring, cyclohexane (C 6 H 12 ), does the
spectrum resemble that of the chains. Note that the presence of more than one
near-edge continuum resonance is also clearly suggested by the EXAFS spec-
trum of cyclohexane shown in Fig. 1.2.
The second piece of evidence against the building block picture for saturated
hydrocarbons is provided by the spectra of long hydrocarbon chains, which
because of their molecular weight are normally solids. The NEXAFS spectra of
long chains in the form of the polymer polyethylene (PE), [-CH 2-CH 2- ]n'
and the Langmuir-Blodgett film cadmium arachidate (CdA),
Cd[C02(CH2)lSCH3]2, on a Si(I11) surface are shown in Fig. 6.20 [6.93-95].
We note, that more recently Ohta et al. [6.96] have obtained higher resolution
spectra for oriented PE than those shown in Fig. 6.20.
The results shown in Fig. 6.20 are for oriented samples in order to take
advantage of angular effects. In the studied PE sample the direction of the
hydrocarbon chains was parallel to the surface as shown in Fig. 6.20a with
rotational disorder around the chain axis. For E along the chain direction the
NEXAFS spectrum exhibits a pronounced resonance around 293 eV, while a
sharp resonance around 288 eV is strongest at grazing X-ray incidence with Eat
a 70° angle from the chain direction. In analogy to the ethane K -shell spectrum,
the 293 eV resonance "B" is assigned to a C-C a* resonance, that at 288 eV,
labelled "A", to a C-H* resonance. In addition to these two resonances a third
resonance "C" is clearly observed, and the difference spectrum (Fig. 6.20b) shows
that this resonance has the same polarization dependence as resonance "B". For
the CdA sample the hydrocarbon chains are oriented perpendicular to the Si
surface (Fig. 6.20c) and the NEXAFS spectra show a remarkable resemblance to
those of PE when the E vector has the corresponding orientation with respect to
the chain direction. The polarization dependence is slightly more pronounced as
revealed by the difference spectrum. Again three resonances are observed with
opposite polarization dependence of resonance "A" and resonances "B" and
"C", respectively. In particular, the identical polarization dependence of reson-
ances "B" and "c" [6.94, 95] indicates a common origin of the two resonances.
Xex-MS calculations for propane reveal the origin of resonances "B" and "c"
in Fig. 6.20. Note that, in retrospect, resonance "c" can also be seen in the
spectra of the paraffins shown in Fig. 6.19, and it appears that its intensity
increases with the chain length. Comparison of the calculated spectra for ethane
and propane in Fig. 6.21 shows that the single C-C a* resonance in ethane splits
into two resonances at and a~ for propane. Because the intensity of the second
192 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

Highly Oriented Polyethylene Cadmium Arachidate/Si(111)

(a)
(c) ~ ~

o~ CdO~
B
(d)

+-m +-

Difference Difference

2BO 290 300 310 320 2BO 290 300 310 320
Photon Energy (eV)

Fig. 6.20a-d. NEXAFS spectra of highly oriented polyethylene and cadmium arachidate. (a)
Schematic of the chain orientation in the sample of highly oriented polyethylene, and blow-up of the
local bonding geometry of a C atom in the chain. The macroscopic chain direction coincides with the
z-axis of the coordinate system and ()( "" 112". (b) Total electron yield NEXAFS spectra of
polyethylene [6.93] for different orientations of the electric field vector E relative to the macroscopic
chain direction and difference spectrum between the normal and glancing (20°) incidence spectra.
Peak "A" is a C-H* resonance, and peaks "B" and "c" are a* C-C resonances. The small peak near
285eV is due to a small amount of unsaturated hydrocarbons (n* resonance), probably on the
surface. (e) Schematic orientation of a monolayer of cadmium arachidate, Cd[C0 2 (CH 2 hs CH 3 ]2 ,
deposited on a Si(I!!) surface by the Langmuir-Blodgett technique. (d) NEXAFS spectra at glancing
(20°) and normal X-ray incidence relative to the Si surface [6.94, 95] and difference spectrum
between the glancing and normal incidence spectra. For both samples the difference spectra clearly
reveal the two C-C a* resonances, shown hatched, the splitting being due to bond-bond inter-
actions in the chain

resonance is considerably weaker, the first resonance is shifted only slightly to

lower energy, such that the center of gravity remains almost unaffected.
This splitting in the (1* system is easily explained in close analogy to that
encountered for the n* system in butadiene. Again we can utilize the concepts of
Sect. 3.4, and with reference to Fig. 3.9 the splitting arises from interaction of the
two adjacent C- C (1 bonds. As for the n system in butadiene the first-order
perturbative interaction between the "localized" (1 bonds in propane leads to a
 6.4 Limitations of the Building Block Picture 193

Fig. 6.21. K-shell excitation spectra of ethane

Xa-MS Theory and propane calculated by means of the X<x-
MS technique [6.78] revealing the effect of
interaction between the adjacent C-C bonds
in propane, namely the splitting into reson-
ances ut and u!. In the shown ethane spec-
trum the artificial glitch at the IP, present in
the spectra in Figs. 4.12 and 6.14, has been
removed

300 310 320

Excitation Energy (eV)

splitting of the anti bonding u* system. There is a remarkable parallelism

between the n* splitting in butadiene discussed in Sect. 6.4.2 and the u* splitting
in propane. In both cases the lowest resonance remains in almost the same
position as that of the building blocks ethylene and ethane, respectively, and the
second resonance is of considerably weaker intensity, resembling a higher-
energy satellite. The origin ofthis resemblance will be discussed in more detail in
Sect. 6.4.6. The experimentally observed u* splitting in propane of about 8 eV
(compare Figs. 6.19 and 6.20) is much larger than the approximately 3 eV
splitting of the n* resonance in butadiene. The ratio of the two splittings is
roughly that estimated by Dewar [6.80] for the ratio of the C-C bond-bond
interaction energies for the u bonds in propane (2.5 eV) and the n bonds in
butadiene (1.2eV). It is the large size of the interaction energy in propane that
led Dewar to refer to the paraffins as u-conjugated.
The question arises why only two u* resonances are observed for the
paraffins with more than three carbon atoms, independent of chain length.
Clearly, a MO treatment of the neutral molecule would predict that the number
of u* orbitals increases with the number of carbon atoms, as shown in Fig. 3.8.
The reason lies in the localized nature of the core excitation which probes the
final state wavefunction near the core of the excited atom. In a perturbative
treatment of the bond-bond interactions in an extended system, the dominant
interaction terms would be between the "localized" bonds of the central excited
atom with its immediate neighbors. The perturbations due to "localized" bonds
associated with more distant atoms would rapidly become smaller with increas-
ing distance. This and related effects associated with the localized nature of the
core hole are discussed in more detail in Sect. 6.4.6.
194 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

The spectra of the saturated hydrocarbon rings shown in Fig. 6.19 also
exhibit a splitting of the 0'* system. For the smallest rings the splitting is more
complicated than that of the chains because the interaction between "localized"
bonds is modified by effects of bond strain and bond- bond interactions across
the rings. Note in particular that the C- C- C bond angle in cyclopropane is only
60° as compared with the ~11O° angle in the paraffins. The origin of the 0'*
splitting in cyclopropane and cyclobutane is clarified in Fig. 6.22 by a com-
parison of experimental and calculated spectra, taken from the work of Horsley
et al. [6.92,97]. In the figure the observed C- C 0'* resonances are also correlated
with specific MOs taken from the book of Jorgensen and Salem [6.34]. As
discussed in Sect. 3.5, the interaction between "localized" 0'* orbitals in cyclo-
propane can be described as being similar to that in the n* system in benzene
and therefore cyclopropane has been called a-aromatic [6.80].

Excitation Energy (eV)

280 290 300 310

3 Gas

1a 29

-10 0 10 20
Energy from IP (eV)

Fig. 6.22. Comparison of experimental and calculated (XIX-MSj K-shell excitation spectra of
cyclopropane and cyclobutane [6.92]. On the right, pictures [6.34] are shown for those molecular
orbitals, labelled by their irreducible representations, which are associated with specific resonances
in the spectra
 6,4 Limitations of the Building Block Picture 195

Experiment

o*c=c
I
Ethylene
'B H..... /H
'c::> H.... C=C'H
~
~
:e
~
Z-
';;;
c:
~ 0*1 0*2
c:

I Allene
Allene
I on
Ag(110)

I I
280 290 300 310 320
Photon Energy (eV) Excitation Energy (eV)

Fig. 6.23. Experimental [6,36, 89] and calculated [6,98] splitting of the aT and a! resonances in
allene, in comparison with the single 0'* resonance in ethylene, The experimental spectra are angle
averaged by summing the respective spectra recorded at 20° grazing and normal X-ray incidence,
normalized to the same edge jump, The splitting is caused by bond-bond interactions of the adjacent
0'* C=C bonds, Note that in allene the H-C-H planes and the 7t systems of the adjacent double
bonds are orthogonal and therefore no splitting of the 7t* resonance exists

0'* bond-bond interactions are not limited to saturated hydrocarbons; they

are also observed in unsaturated systems. This is illustrated in Fig. 6.23 for
interacting C=C 0' bonds. In going from ethylene (H 2 C=CH 2 ) to allene
(H 2 C=C=CH 2 ) a splitting of the 0'* resonance is observed. The experimentally
observed splitting is remarkably large, ~16 eV, about twice that found in the
paraffins.
For the case of weakly chemisorbed allene on Ag(llO) shown in the figure
the observed splitting is identical to that found in free [6.99] allene. This
splitting is also clearly revealed in the spectra calculated by the Xoc-MS method
for ethylene and allene [6.78], shown in the same figure, although the magnitude
of the calculated splitting is only about 11 eV. Note that the 1t orbitals of the two
C=C double bonds in allene are orthogonal and therefore only the 0'* system is
split. The splitting in allene is again due to the interaction between the two
"localized" C=C 0'* orbitals. Its larger size relative to propane is mainly a result
of bond length, which is shorter in allene (1.308 A) than in propane (1.526 A).
Therefore the strongly distance-dependent interaction between the two "local-
ized" bonds is significantly increased in allene. This will be discussed in more
detail in Chap. 8.
196 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

C K-edge Carbon Dioxide

OK-edge
11'* (a) 11'* (b)
Experiment
xv.. 0* 02*

iC
:::I IP
.e.!!!. 11'* Theory
.~ 0* 11'*
!II
C

~
02*

290 300 310 320 530 540 550 560

Excitation Energy leV)

Fig. 6.24. Experimental [6.17, 104] and calculated [6.78] K-shell excitation spectra of carbon
dioxide (O=C=O), at the C and 0 K-edges. At the 0 K-edge two a* resonances are observed due to
interactions of the adjacent C=O bonds. The resonances labelled at and a! correspond to
transitions to the Sa: and 4a: MOs, respectively, which are depicted in Fig. 3.2. At the C K-edge the
transition to the lower-energy Sa: orbital is forbidden by the dipole selection rule due to inversion
symmetry and thus only one a* resonance is observed

Finally we discuss the spectra of three molecules with multiple

carbon-oxygen bonds, namely carbon dioxide (C0 2 ), and the formate
(HCOO-) and carbonate ([C0 3]2-) anions, which can be isolated on surfaces.
We shall start with the C and 0 K-shell spectra of CO 2 , shown in Fig. 6.24,
which have been the subject of considerable dispute in the literature
[6.100-103]. At first sight, the spectra are in conflict with both the simple
building block picture and the simple bond-bond interaction picture used above
for the paraffins and allene. In the building block picture, the two identical intra-
molecular C=O bonds should give rise to only one 0'* resonance, while two 0'*
resonances should be observed if interaction between the two adjacent C=O
bonds is considered. In contrast, there is one 0'* resonance in the experimental C
K -shell spectrum and two 0'* resonances, labelled at and a!, in the 0 K -shell
spectrum. The exact energy position of the a! resonance is unclear because of
shake-up structure in that spectral region.
The answer to the puzzle is provided by symmetry considerations [6.102].
Similar to allene, carbon dioxide consists of two adjacent unsaturated bonds,
and interaction between these C=O bonds causes a splitting of the 0'* system. In
contrast to allene, however, CO 2 possesses inversion symmetry about the
 6.4 Limitations of the Building Block Picture 197

central carbon atom, and therefore one of the possible a* transitions is sym-
metry forbidden for C K-shell excitation. We have already encountered the
HOMO and LUMO MOs for CO 2 in Sect. 3.2.1, and as shown in Fig. 3.2, there
are two a* orbitals arising from interaction of the adjacent carbon-oxygen
bonds, the 5a: MO, which is gerade with respect to inversion about the carbon
atom, and the higher-energy 4a: MO, which is ungerade with respect to
inversion and hence contains a node at the carbon position. For carbon K-shell
excitation the transition to the lower-energy 5a: MO is symmetry forbidden as
discussed in Sect. 3.6.3. This is directly seen from the orbital contour plot in Fig.
3.2, which exhibits no node and therefore no p-character at the carbon site. On
the other hand, a transition to the higher-energy 4a: MO is symmetry allowed
because the orbital has a node and hence p-character at the carbon position.
Thus in the C K -shell spectrum the observed a* resonance corresponds to a
transition to the higher-energy 4a: MO. For the 0 K-shell, transitions to both
the 5a: and 4a: MOs are allowed because both MOs have nodes at the oxygen
positions, and the two transitions correspond to the two resonances labelled aT
and a! in Fig. 6.24. Results obtained with the Xa-MS technique [6.78], also
shown in Fig. 6.24, are in good agreement with the simple expectations from
MO theory and experiment. We mention that the above assignment of the K-
shell resonances is also in agreement with ab initio calculations [6.105-107].
In principle, bond-bond interactions also exist within the n* system of CO 2 •
However, as indicated in Fig. 3.2, the lower Ing antibonding orbital is occupied
such that only one n* resonance, corresponding to a transition to the 2n: MO,
is observed at both the carbon and oxygen K-edges.
The formate anion (HCOO-), which can be produced on surfaces by
dehydrogenation of formic acid (HCOOH) [6.52], is characterized by two
identical C=O bonds, approximately 1.28 A in length (Sect. 8.6.5). In contrast to
CO 2 , there is no inversion symmetry about the C atom. The C K-edge NEXAFS
spectrum of formate on Ag(llO) [6.108], shown in Fig. 6.25a, therefore exhibits
two a* resonances, separated by about 3.3 eV. The lower energy aT resonance
dominates at grazing X-ray incidence and the a! resonance at normal X-ray
incidence. These resonances originate from transitions to the 8a l and 5b 2 MOs
(C 2v symmetry) shown in Fig. 6.25b, respectively. Since the 8a l MO component
on the C atom is directed along the C-H bond and the 5b 2 MO points in the
direction of the 0-0 axis, the polarization dependence of the spectra indicates
that the molecular plane, on the average [6.108], is perpendicular to the surface
(the molecule bonds in a bidentate configuration via the two 0 atoms).
The splitting of the a* system into the 8a l and 5b 2 MOs is caused by the
interactions of the two adjacent C=O bonds, and the symmetry of the two MO
components is also reproduced by Xa-MO calculations of HCOO- [6.98],
shown in Fig. 6.25c. In accordance with the observed spectra and the MO
picture the lowest a* resonance is observed when the E vector lies along the
C-H bond (z-axis), and the higher-energy resonance appears for E along
the 0-0 axis (y-axis). The calculated splitting is, however, smaller (1.2eV) than
 198 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

Experiment: HCOO/Ag(110) Xo<-MS Theory: HCOO-

11"" (a) H (b) r

I
(c)

o~~~~
I
I
a*2 5b 2 I
I
Sum
~
.~ j ,
·c:J
~

C>~~~=
C I tz
'" I 8c----y
,
~ ~ I
~ a"1 8a 1 ~ I o~r~o
:e .~
.c I
~/
Ix Ellx
'"
.O. . . .~0c,O
;::
.;;;
;::
.;;;
§ 1.""'•.ttttIHfL·1;I-'-=' C

o
C-H 00<> "00 7a 1 $
C
0 C

"Elly

'1r*
000
o-c_o 2b,
000
280 290 300 310 320 285 290 295 300 305 310
Photon Energy (eV) Excitation Energy (eV)

Fig.6.25. (a) Polarization-dependent C K-edge spectra offormate (HCOO) on Ag(llO) at 300 K for
a coverage of about 0.5 monolayers and curve fits [6.108]. (b) Unoccupied molecular orbitals
obtained from a MO calculation of HCOO/Cu(llO) [6.109]. The symmetry label on the left is with
respect to the plane containing the atoms, and it establishes the link to the observed resonances. The
irreducible representations of the orbitals in C 2y symmetry are given on the right, where the labelling
according to Table 3.1 refers to the coordinate system in (c). (c) Polarization-dependent spectra
calculated by means of XOt-MS theory [6.98], using the shown coordinate system

the observed (3.3 eV) separation. The calculations were carried out using the
transition state method and used the sphere overlap determined by matching
experimental and calculated IPs at the C K-edge in CO 2 •
As a last example of the effects of bond-bond interactions we consider
the carbonate, (C0 3)2-, anion. The polarization-dependent C and 0 K-edge
NEXAFS spectra of carbonate on Ag(llO) [6.110] are shown in Fig. 6.26.
Similar results were obtained by Bader et al. [6.111], showing that the molecule
lies flat on the surface. The C K-shell spectrum exhibits a n* and a single u*
resonance, approximately 10eV higher. The 0 K-edge spectrum also exhibits a
n* and a lOeV higher u* (labeled un
resonance, but an additional u* resonance
(labelled ut) is observed between the two resonances. Again, as in CO 2 , this
observation is in good accord with a bond-bond interaction picture and
restrictions imposed by the dipole selection rule.
The carbonate anion is flat in its ground state with D3h point group
symmetry. The lowest unoccupied MOs are of 2a 2(n*), Sa'l (u*), and Se' (u*)
symmetry [6.111], the splitting of the u* system again arising from interactions
of the C=O bonds. For C K-shell excitation only the 2a'1 -+ 2a 2(E perpendicu-
lar to molecular plane) and 2a'1 -+ Se' (E in molecular plane) transitions are
allowed. At the 0 K-shell all three transitions are allowed because the 0 Is
orbital belongs to both the a~ and e' representations. These symmetry consid-
erations are supported by the results ofXoc-MS calculations [6.98J shown at the
 6.4 Limitations of the Building Block Picture 199

C K-edge OK-edge

(a) Experiment: (b) Experiment:

C0 3/Ag(110) C0 3/Ag(110)
u'2

±
Theory:
(C0 3)2-

tLS

280 290 300 310 320 520 530 540 550 560
Photon Energy (eV)

Fig. 6.26. Polarization-dependent NEXAFS spectra for carbonate (C0 3 ) on Ag(llO) at the C K-
edge (a) and 0 K-edge (b) [6.110], and results ofaXIX-MS calculation for the carbonate anion
(C0 3 f- [6.98]

bottom of Fig. 6.26. Here we have labeled all resonances to facilitate the
comparison of experimental and calculated spectra. The agreement is striking,
except for a step-like background in the experimental 0 K -edge spectrum. As
discussed in Section 7.4.3, this step is due to hybridization of molecular and
metal states. The fact that it occurs only at the 0 K-edge indicates that
carbonate preferentially bonds to the surface via the 0 atoms, as in bulk
carbonates [6.112].

6.4.4 Aromatic Rings: Benzene and Related Molecules

If the building block picture were extended to benzene (C 6 H 6 ), one would expect
to find only one n* and one u* resonance in its NEXAFS spectrum because of
the equivalence of all carbon-carbon bonds with a bond length of 1.396 A. The
NEXAFS spectrum of benzene, however, exhibits two pronounced n* and u*
resonances. This is clearly revealed by Fig. 6.27 where the NEXAFS spectra for
ethylene (C zH 4 ) [6.113] and benzene [6.114, 115] chemisorbed on Ag(110) are
compared. For our discussion we have purposely chosen the weak chemisorp-
tion systems shown in Fig. 6.27 because the silver surface orients the molecules
without distorting them. Thus the spectra exhibit the characteristic molecular
resonances, and their polarization dependence allows us to separately investig-
ate the n* and u* resonances. It is evident from Fig. 6.27 that both molecules lie
200 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

Fig. 6.27. Carbon K-edge NEXAFS spectra

(a) rr'
of ethylene (C 2 H 4 ) [6.113] and benzene
(C 6 H 6) [6.115] monolayers on Ag(llO). The
splitting of the n* and 0"* resonances in
benzene is caused by bond-bond interaction
ME of the respective n* and 0"* antibonding or-
I bitals in the molecule. As revealed by the
I polarization dependence of the spectra, both
molecules are bonded to the surface via their
n orbitals such that the C-C bonds are ap-
proximately parallel to the surface. Note
that the C6H6/ Ag(llO) surface was prepared
by annealing a multilayer to 180 K [6.115].
Under these conditions benzene appears to
be slightly tilted as evidenced by the non-
~ vanishing n* resonance at normal incidence
en
c:
~ ~~~~~~~~~~~~~~~~

290 300 310 320

Photon Energy (eV)

down on the surface such that the n* resonances dominate at grazing X-ray
incidence (E vector 20° from surface normal) and the 0"* resonances are
strongest at normal X-ray incidence.
Close inspection of the grazing incidence spectra in Fig. 6.27a reveals that
the single n* resonance in ethylene is split into two for benzene. In fact, a third,
weaker peak, labelled "ME" is observed in the benzene grazing incidence
spectrum. This peak coincides in position with the first 0"* resonance and,
following a first-principles calculation [6.116], is assigned to a multi-electron
feature associated with the n system.
At normal incidence, the benzene spectrum exhibits two 0"* resonances,
rather than the expected one, as observed for ethylene. The presence of two 0"*
resonances is not specific to chemisorbed benzene since the same two resonances
are also observed for free and condensed benzene molecules as shown in Fig.
6.28a. Close inspection of the spectra of free and condensed benzene reveals that
the higher energy 0"* resonance has two components. As for propane and allene
discussed earlier, these resonances signify a breakdown of the simple picture
which associates each 0"* resonance with a specific bond.
The explanation of the NEXAFS spectrum of benzene is provided by a Xc<-
MS calculation (Fig. 6.28c), which shows that multiple resonances may result
 6.4 Limitations of the Building Block Picture 201

la) Experiment C6H6 Ib)

C(1 5) --'---'--

c
o
"E
Ql
(fJ
-----,..,--~--~J r/)
r/)
o
U

Excitation Energy (eV) Energy reI. to IP (eV)

Fig. 6.28. (a) Carbon K-edge NEXAFS spectra of benzene (C 6 H 6 ), in the gas phase [6.118],
condensed as a multilayer [6.115], and chemisorbed on Ag(110) [6.114, 115]. (b) Antibonding it·
molecular orbitals associated with the observed resonances, labelled by their irreducible representa-
tions. (c) The spectrum calculated by means of the XIX-MS method [6.117]

from "resonance" interactions between localized molecular states [6.117]. For

benzene and other aromatic molecules there is a strong interaction between the
localized n* and u* states, producing a set of delocalized orbitals which are
significantly separated in energy. In fact, for benzene there are two n* and
several (at least three [6.117]) u* antibonding orbitals, giving rise to two strong
transitions to n* and u* states, respectively. The MOs associated with the
observed n* resonances are depicted in Fig. 6.28b [6.34].
Similar splittings are also observed for other aromatic molecules which
are based on the phenyl ring such as toluene (C6HSCH3) [6.119], aniline
(C 6HsNH2) [6.115], phenol (C 6H sOH) [6.115, 120], monofluorobenzene
(C6HsF) [6.118], or benzenethiol (C 6H sSH) [6.121, 122]. In such systems,
symmetry reduction and/or chemical shifts associated with the ligand group
lead to a further splitting of the n* system, relative to benzene, as shown in
Fig. 6.29 for aniline, phenol, and monofluorobenzene. The degenerate e2u orbital
in benzene (Fig. 6.28b) is split into a 2 and b l MOs in these latter molecules as
indicated in Fig. 6.29b. This splitting is small « 1 eV), however, as discussed in
detail by Solomon et al. [6.115]. On the other hand, the Is binding energy of the
C 1 atom is larger than the average binding energy of the C 2, C 3, and C4 atoms
by 1.2eV for aniline, 1.6eV for phenol, and 2.0eV for monofluorobenzene [6.35,
202 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

(a) 1t1,2 (b)

1t3,4
I
0
", .. /

280 290 300 310 320

Excitation Energy (eV)

Fig.6.29. (a) NEXAFS spectra of condensed benzene, aniline, and phenol [6.115], and the ISEELS
spectrum of monofluorobenzene gas [6.118]. The labelling of the 1t* resonances follows the
transition scheme shown in (b). For the substituted benzene molecules the e2u MO in benzene splits
into a 2 and b l MOs and the C Is core level binding energies for the individual carbon atoms in the
ring differ as indicated. Within the resolution of the experimental spectra only the four indicated
transitions are observed

115]. This leads to the spectral assignment shown in Fig. 6.29. Higher resolution
spectra are expected to exhibit additional splittings owing to the splitting
between the a 2 and b i MOs and the small chemical binding energy shifts
between the C 2 , C 3 , and C 4 atoms [6.115].
Other heterocyclic aromatic rings such as pyrrole (C 4 H 4 NH) [6.121, 123],
furan (C 4 H 4 0) [6.121, 123, 124] or thiophene (C 4 H 4 S) [6.121, 123, 125, 126]
also exhibit a splitting of the n* and 0'* resonances. In particular, pyridine
(CsHsN) has been extensively studied [6.117, 119, 127, 128] and its spectrum at
both the carbon and nitrogen K -edges closely resembles that of benzene. Other
related K -shell studies are those of molecules with more than one phenyl group,
such as naphthalene [6.90], the poly-phenylenes [6.88, 129], and polyacenes
[6.88]. Finally, the close resemblance of the K-shell spectra of borazine
(B3N3H6) and benzene should be mentioned, which has been used to prove the
aromatic character of the bonding in borazine [6.130].

6.4.5 Crystalline Solids

In the form of graphite and diamond, nature provides us with crystalline solids
of well-known bonding and structure. It is interesting therefore to compare the
 6.4 Limitations of the Building Block Picture 203

(a) Diamond Benzene Graphite

~
Cyclohexane ~

.#it ~
(b) (e)

Solid 1T* Bands

Benzene

Graphite

Solid
Cyclohexane

Graphite

280 290 300 310 320 280 290 300 310 320
Photon Energy (eV)

Fig. 6.30a;:. NEXAFS spectra of graphite and diamond in comparison to those of the molecular
"building blocks" benzene and cyclohexane. (a) Structural models for diamond, benzene, cyclo-
hexane, and graphite. Note that in diamond and cyclohexane all bonds are arranged tetrahedrally
(Sp3 hybridization, bond angle "" 110 The C-C skeleton in cyclohexane also exists in the diamond
0
).

lattice. For benzene and graphite the C atoms are in planes and trigonally coordinated (Sp2
hybridization, bond angle 120°). (b) NEXAFS spectra of solid benzene [6.115], graphite (recorded at
the magic angle to eliminate angular effects), solid cyclohexane, and diamond [6.131]. In the spectra
n*, C-H*, and <1* features can be distinguished, as indicated. (e) Polarization dependence of the
spectra for benzene, adsorbed at submonolayer coverage with its plane parallel to a Ag(llO) surface,
and for highly oriented pyrolytic graphite, where the ring planes are parallel to the macroscopic
surface. The spectra at grazing and normal X-ray incidence emphasize resonances associated with
the· n* and <1* derived levels or bands, respectively

K-shell spectra of these solids to those of molecules which exhibit a similar

bonding and local structure. As illustrated in Fig. 6.30 the molecules benzene
(C6H6) and cydohexane (C 6H 12 ) may indeed be regarded as building blocks for
graphite and diamond, [Link]. Benzene and graphite are both Sp2 hybri-
dized and each carbon is trigonally bonded to three other atoms, with all bonds
in a plane and 120 bond angles. The C-C bond lengths are also similar, 1.396 A
0

for benzene and 1.421 A for graphite. Graphite can thus be envisioned as
benzene rings without hydrogens, linked together by strong covalent bonds in a
two-dimensional planar network. Weaker van-der-Waals forces between the
individual parallel planes lead to the characteristic layered structure of graphite.
204 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

The bonds in diamond and cyclohexane, on the other hand, are Sp3 hybridized,
and each carbon atom is bonded tetrahedrally to four neighbors, as illustrated
by the four black atoms in the diamond lattice in Fig. 6.30a. The bond angles
between any three atoms is about 110°. The C-C bond lengths are 1.535 A in
cyclohexane and 1.544 A in diamond. From inspection of Fig. 6.30a it is
apparent that the diamond lattice can be constructed from the carbon skeleton
in cyclohexane.
The K-shell spectra of solid benzene, graphite, solid cyclohexane and dia-
mond are compared in Fig. 6.30b. In general, for hydrocarbons the NEXAFS
energy range can be subdivided into three regions characterized by specific
resonances: The first n* resonance around 285 ± 1 eV, C-H* resonances around
288 ± leV, and a broad 0'* region between 290eV and 315eV, as indicated in
the figure. As shown in Fig. 6.30 the existence of the n* and C-H* resonances
can clearly be used to establish the hybridization of the C-C bonds in all cases
and the existence of C-H bonds in the samples. Benzene and graphite have
unsaturated C-C bonds, as proven by the n* resonance in their spectra, and
graphite and diamond do not contain hydrogen, as is evident from the missing
C-H* resonance. In particular, the n* resonance may be used to clearly dis-
tinguish the two forms of carbon from each other. This characteristic feature can
be utilized, for example, for determining whether the local bonding in (hydro-
genated) amorphous carbon films is graphitic or diamond-like [6.131].
In contrast to the characteristic n* and C-H* resonances which can serve as
a fingerprint of the local bonding, the 0'* region is more complex. Clearly,
despite the similarity in hybridization and bond lengths of benzene and graphite
on one hand and cyclohexane and diamond on the other, there is no direct
indication of this fact in the respective spectra. The reason for the loss of
correlation between local bonds and 0'* resonances lies in the formation of
electronic energy bands in graphite and diamond by interaction oflocal states in
a periodic potential. As first shown by Muller et al. [6.132] for metals and later
for diamond and graphite by Weng et al. [6.133, 134], the near-edge fine
structure in such cases is determined by the appropriate angular momentum
projection of the crystalline density of states. In a scattering picture this is
equivalent to summing over all scattering paths of the excited photoelectron in
the lattice. Thus the long range periodicity of the lattice leads to strong
contributions from scattering events involving distant neighbors, which signific-
antly distort the structure arising from scattering processes involving only the
nearest neighbor atoms. Scattering events from distant neighbors can contribute
in NEXAFS because the excited photoelectron has a small kinetic energy and
therefore a long mean free path (Fig. 5.6).
Band-structure effects, or in a different picture, long-range scattering pro-
cesses, are so important in graphite and diamond largely because of the rigidity
of the lattices, resulting in small vibrational amplitudes of the atoms. The mean-
square vibrational amplitudes 0'2 are about 2.5 x 10- 3 A2 in diamond [6.135]
and un = 3.1 x 10- 3 A2 in the basal plane and O'i = 1.4 x 10- 2 A2 perpendicu-
lar to the basal plane in graphite [6.136]. Because of the larger mean-square
 6.4 Limitations of the Building Block Picture 205

displacements in polymers, long range scattering effects are much weaker and
the nearest neighbor contributions dominate. For example, for polyethyl-
ene values of ai = 4 x 10- 2 A2 perpendicular to the chain direction and
an = 1 x 10- 2 A2 along the chain direction have been found [6.137]. Note that
even the smaller mean-square displacement (along the chain direction) in
polyethylene is still large and comparable to the motion between the van-der-
Waals bonded planes in graphite.

6.4.6 Effects of Core Hole Localization

The localized nature of the K -shell excitation process has many important
consequences. We have already encountered examples of the significance of
these "localization" effects in previous chapters. In Chap. 2 we discussed the
importance of the core hole for the quantitative description of the K-shell "line
widths" and the binding and transition energies. In Chap. 3 it was shown that
the symmetry and localization of the 1s initial state has important consequences
for the dipole transition matrix element. It became apparent in Chap. 4 that the
systematics of the energy positions of the various near edge resonances crucially
depends on the localization of the 1s orbital and the core hole. In fact, K-shell
spectra of molecules are significantly simpler than ultraviolet absorption spectra
for this very reason.
We now address the importance of the core hole for the understanding of
resonance positions and intensities in K-shell spectra of large molecules and
solids. Again, we have already encountered an important example, the building
block picture. The direct correlation between core hole localization and K-shell
resonances is best illustrated by Fig. 6.13. While it is easy to understand that
localized excitations in nonconjugated systems lead to preferential excitations to
certain molecular orbitals it is, at first sight, not obvious that related effects
should also exist for conjugated systems or even crystalline solids. Below we
shall show that core hole localization effects are important even in such systems.
From the n* electron affinity data shown in Fig. 3.7 one would have
expected a split n* resonance in butadiene with the first n* resonance position
about 1.1 eV lower than that in ethylene (284.7eV) and the second one higher
than that in ethylene by about the same amount. This is not observed. The first
n* resonance position in butadiene (~284.5 eV) is almost identical to that of
ethylene, as shown in Fig. 6.15. Also, the splitting in the K -shell spectra (~3 eV)
is somewhat larger than that observed in the electron affinity data (~2.2eV).
Finally, in the K -shell spectra most of the oscillator strength remains in the first
n* resonance, the second one resembling a higher-energy satellite. Similar effects
are observed in Fig. 6.16, where the K-shell spectrum of 2,4-hexadiyne is
compared to that of methylacetylene.
These observations for the n* positions and intensities are a direct conse-
quence of core hole localization effects, as first discussed by Robin et al. [6.90] in
their comparison of the n* resonance positions of ethylene, butadiene, benzene,
and naphthalene. Similar arguments have been used by Yokoyama et al. [6.88]
206 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

in their study of the poly-p-phenylenes and polyacenes. In contrast to other

measurements on the valence orbitals such as photoemission and electron
transmission spectroscopy, the K-shell spectra need to be interpreted by use of
the equivalent core model. In the case of hydrocarbons, excitation of a specific
carbon atom results in an excited state which is well described by the replace-
ment of the excited carbon atom by nitrogen, as discussed in Sect. 2.4. Because of
the dipole selection rule, NEXAFS probes the 2p component of the unfilled
valence orbital. Since the 2p level of nitrogen is lower in energy (~2 eV) than
that of carbon, the lowest n* orbital becomes concentrated at the excited carbon
atom. Viewed in this way, the position of the n* resonance relative to the 1s
ionization potential is then determined mostly by the 2pn atomic ionization
potential of the pseudo-N atom, and thus becomes independent of the molecular
size. Also, since the transition intensity is largely determined by the density of
the 2pn* orbital on the excited atom, the lower energy n* resonance will be
strongest.
The above arguments also apply to u* resonances in conjugated systems.
The correspondence of bond-bond interactions in butadiene and propane in
Fig. 3.9 is remarkably well reflected by the respective K-shell spectra, if we
exchange the n* and u* labels. As shown in Fig. 6.21, in propane the lowest
energy u* resonance is almost unshifted from that in ethane and it contains most
of the oscillator strength, in direct analogy to the n* resonances in butadiene
and ethylene. This can again be explained by the localized nature of the core
hole, rendering the excited carbon atom nitrogen-like. Similar to the n* system,
the position of the u* system is determined by that of the 2p and 2s orbitals of
nitrogen. Again, the transition intensity to higher u* orbitals resulting from
bond-bond interactions is reduced because they have less density on the core
excited atom. This picture also explains why the spectra oflonger alkane chains,
e.g., polyethylene shown in Fig. 6.20, resemble those of propane. Although the
number of C-C u* orbitals increases with the chain length, transitions to these
higher energy orbitals are not seen in NEXAFS because they do not have a
significant density on the excited atom, due to core hole localization effects.
Finally, we mention that core hole localization effects have also been
discussed for solids. It has been argued by Mele and Ritsko [6.138] that core
hole localization is responsible for the energy position and shape of the n*
resonance in graphite (Fig. 6.30). These authors found that the calculated
density of empty n states of the unexcited solid could not account for the
measured n* resonance position and line shape. On the other hand, inclusion of
the core hole, resulting in loss of the translational symmetry of the graphite
lattice and a local distortion of the crystal potential, led to a downward shift and
pile-up of the density of states near the bottom of the band, in good accord with
experiment. In this model the n* resonance in graphite was linked to a strongly
localized Frenkel exciton. Mele and Ritsko's results have been questioned by
Weng et al. [6.133], who obtained good agreement between the measured nand
u near edge structures of graphite and the p-projected density of states. The
latter authors did not have to evoke core hole effects.
 6.5 Assembly of Functional Groups to Macromolecules 207

Whatever the size of possible core hole effects in solids, it appears clear that
they are considerably smaller than in free molecules. As pointed out by Jugnet
et al. [6.22], the electron-hole interaction energy is greatly reduced in solids. For
example, we have shown in Sects. 2.4.2 and 4.2.2 for free CO that the position of
the 2n* level relative to the vacuum level is about 10 eV lower in the core excited
molecule than for CO in its ground state. For graphite on the other hand, the
lowest unfilled flat n band is 1.6-3 eV above the Fermi level [6.133, 139] while
the n* resonance lies 0.65 eV above the Fermi level as judged from the 285.35 eV
n* resonance position [6.140] and the 284.7 eV Is binding energy [6.141]. This
would imply an electron-hole interaction energy of only about 1-2 eV. This
small value implied by the' above results is also in good accord with the small
excitonic binding energy observed for the K-shell spectrum of diamond by
Morar et al. [6.142] (Sect. 7.4.2).

6.5 Assembly of Functional Groups to Macromolecules

In recent years the structure and bonding of thin polymer films on metal surfaces
have attracted a lot of attention, and many NEXAFS studies of such systems
have been performed [6.143-153]. Such films are of great technological import-
ance with applications in the packaging of electronic devices [6.154], and in
displays, organic batteries and solar cells [6.155].
In our effort to understand and predict the NEXAFS spectra of macromole-
cules and polymers that are composed of various functional subgroups it is
useful to come back to the building block picture one more time. Despite its
failure in conjugated systems and crystalline samples with long range period-
icity, we may try a modified version of the building block picture for large
molecules. The idea is to decompose large polyfunctional molecules into weakly
interacting functional subgroups and then account for the spectra of the
macromolecule by addition of the spectral "fingerprints" of the subgroups,
which may include the effects of conjugation. Within this picture the signatures
of functional groups are taken to depend only upon the local intra-group bonds
and not upon inter-group bonds.
As an example we consider in Fig. 6.31 functional groups containing c-o
bonds such as carboxylic acids and esters. Here spectra are shown for a variety
of molecules containing the carboxylate group (-C0 2-) ranging from gaseous
formic acid [6.91] and gaseous methyl formate [6.73] to the polymer poly-
methylmethacrylate (PMMA) [6.77]. Each of the C K-edge spectra exhibits
three peaks which are characteristic of the carboxylate group. The first peak is
the sharp C=O n* resonance at approximately 288eV, the second the C-O u*
resonance at 296eV, and the third the C=O u* resonance at 302eV. The
differences in the region between 290 and 295 eV arise from changes in the
RydbergjC-H* resonances, as expected. In PMMA all resonances are less
pronounced because of the many different environments of C in this polymer.
208 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

Fig. 6.31. K-shell excitation spectra of various

molecules containing the carboxylate group
1T-
C=O (-C0 2 -). (a) IS EELS spectrum of gaseous for-
mic acid [6.91]; (b) ISEELS spectrum of gaseous
methyl formate [6.73]; and (c) NEXAFS spec-
U> trum of polymethylmethacrylate, PMMA
.t::
c:
~ ac~ [6.77]. All spectra contain the three labelled
~ resonances which are characteristic of the car-
...
~
H
I boxylate group
:e t>
...'">
•0;;
(a) H
I

...'"[Link] C=O
bat 3
(b)

290 300 310 320

Excitation Energy (eV)

Especially the hydrocarbon backbone contributes "background" intensity in the

spectrum above 286eV, as is evident from Fig. 6.19.
As a final example, let us discuss the C K -edge NEXAFS spectrum of
polyimide (PI) [6.147], an important polymer with extensive use in the micro-
electronics industry [6.154, 156]. In its most common form, polyimide consists
of oxydianiline (ODA) and pyromellitic dianhydride (PMDA) subgroups as
shown in Fig. 6.32d. Here we shall simply restrict ourselves to understanding the
n* region of the NEXAFS spectrum of PMDA-ODA PI shown in Fig. 6.32d.
We therefore need to consider the n* fingerprints of all unsaturated subgroups.
The spectrum of ODA should resemble that of phenol shown in Fig. 6.29 or
that of the polymer poly(dimethyl phenylene oxide) (PM PO) shown in Fig.
6.32a, and, as expected, the spectra of phenol and PMPO are very similar. The
n! resonance (cross-hatched) is larger relative to the ni resonance (dashed) in
PM PO because two of six carbon atoms are bonded to oxygens in PMPO,
rather than one out of six in phenol and ODA. Also, the energies of the ni and
n! resonances in PMPO are slightly higher than those in phenol (and ODA).
The second large building block is PMDA. It consists of C = 0 groups and a
benzene ring. The C = 0 n* resonance should lie near 287 eV, judging by the n*
position in formaldehyde (286.0eV, Fig. 4.5 and Table 4.1) and formic acid
(288 eV, Fig. 6.31). Indeed, the NEXAFS spectrum of the polymer poly(vinyl
methyl ketone) (PVMK) shown in Fig. 6.32b exhibits a single n* resonance
(dotted shading) near 287 eV, as expected from its structure, which is also given
in the figure.
Benzene should give rise to a n* resonance near 285 eV as shown in Fig. 6.28.
The spectrum of the polymer PMDA-MBCA PI (MBCA stands for methylene
 6.5 Assembly of Functional Groups to Macromolecules 209

(a)
PMPO

(b )
PVMK

~
Q)
:;:::
c PMDA-MBCA PI
e
u
foio-~NI
--
Q)
ijj
~
ttl
"0 PMDA
C
o
()
Q)
(/)

ODA

280 285 290 295 300 305

Photon Energy (eV)

Fig. 6.32. C K-shell NEXAFS spectra of several complex polymers with functional groups that
occur in polyimide (PI) [6.147]. In its most common form, polyimide consists of oxydianiline (ODA)
and pyromellitic dianhydride (PMDA) subgroups (PMDA-ODA PI) and the structure and spec-
trum are shown in (d). The polymer poly(dimethyl phenylene oxide) (PM PO) shown in (a) is a model
compound for the ODA group in PMDA-ODA polyimide. Its n* resonances are similar to those of
phenol (Fig. 6.29). The NEXAFS spectrum of the polymer poly(vinyl methyl ketone) (PVMK) shown
in (b) exhibits the characteristic n* resonance of a C=O group (dotted shading). The n* resonances in
the spectrum of the polymer PMDA-MBCA PI (MBCA stands for methylene bis-cydohexyl amine),
shown in (c), correspond to the PMDA group. The resonance with dotted shading is that of the c=o
group, and that characteristic of benzene (Fig. 6.28) is shown black. The spectrum of PMDA-ODA
PI shown in (d) contains the n* resonances of all building blocks, as indicated by the shading

bis-cyclohexyl amine) shown in Fig. 6.32c, which contains the conjugated

PMDA unit as the only unsaturated subgroup, shows this resonance, shaded
black, as expected. It also exhibits a C=O resonance, shown in dotted shading. It
is interesting to point out that the black resonance is shifted to lower energy
than in benzene, while the dotted resonance is shifted to higher energy than in
PVMK. This is attributed to the interaction of the benzene and C=O n* systems
in PMDA, in analogy to the observations presented in Fig. 6.l7a for propiolic
acid. The n* resonances in the spectrum of PMDA-ODA PI shown at the
bottom of Fig. 6.32 can now be assigned as indicated by their shading code.
Many other examples can be cited to show that the NEXAFS spectra of
complex polymers closely correspond to those expected from the spectra of the
210 6. Spectra of Condensed, Chemisorbed, and Polymeric Molecules: An Overview

various functional subgroups. In fact, NEXAFS spectroscopy of thin electro-

chemically deposited layers has already revealed important new information
with regard to the orientation of such layers [6.143-152]. In the future much
more work in this area, which is not specifically covered in this book, can be
expected.
7. Analysis of K-Shell Excitation Spectra by Curve Fitting

Below we review methods for the quantitative analysis of NEXAFS spectra.

Theoretical expressions are given for the lineshapes offeatures, such as steps and
peaks, that are commonly encountered in NEXAFS spectra. Also, we discuss
general guidelines for the positions and shapes of characteristic features.

7.1 The Need for a Quantitative Analysis

This chapter describes procedures for the quantitative analysis of K-shell

excitation spectra based on curve fitting techniques. We have already encoun-
tered an example of such an approach in Fig. 2.1 b, one of the early attempts to
account for the various components in an X-ray absorption spectrum. With
only a few notable exceptions [7.1-3], curve fitting was not extensively employ-
ed in X-ray absorption spectroscopy and ISEELS until about 1988, when Outka
and Stohr [7.4] applied it to the K-shell spectra of low-Z molecules. Arvanitis
et al. [7.5] have extended this model by introducing a line shape function based
on a physical scattering model.
The curve-fitting procedures discussed below are based on the deconvolu-
tion of peaks and steps in the spectra and an understanding of the lineshape and
parameters describing the peaks and steps. For this purpose we use a data base
consisting of a large variety of molecules and molecular units in different
environments, namely gases, adsorbates and solids. The systematic method
described here oflocating peak positions and intensities of near edge resonances
is essential for the accurate determination of bond lengths (Chap. 8) and
molecular orientations (Chap. 9). Our goal is to provide a consistent formalism
for analyzing such spectra, to summarize some of the guidelines in fitting core
excitation spectra which have been found empirically, and to gain insight into
the physical processes occurring during the core excitation event by examining
general trends.

7.1.1 Curve Fitting of Original Spectra

The basic ingredients for curve fitting of X-ray absorption spectra, namely peaks
and steps, are revealed by Fig. [Link], where the early attempt by Parratt [7.1] is
shown to quantitatively account for the K-shell spectrum of argon gas. For free
212 7. Analysis of K-Shell Excitation by Curve Fitting

atoms or molecules, steps occur at the IPs as discussed in Sect. 4.2.1 in

conjunction with Fig. 4.2. Peaks or resonances occur at energies below the IP,
corresponding to bound state transitions and also, superimposed on the con-
tinuum step, at energies above the IP.
The deconvolution of the near edge core excitation spectra is accomplished
by performing nonlinear least-squares fitting [7.6] on the experimental data. In
this process, each of the peaks or steps in a spectrum is approximated by a
particular lineshape, which in turn is defined by a number of variable para-
meters such as position, height, and width. The entire spectrum is considered
then to be a sum of the various lineshapes. The choice of a lineshape to describe
a spectral feature is based either upon a physical model or simply what function
appears to fit the experimental data the best.
NEXAFS spectra are typically recorded as a function of X-ray incidence and,
in principle, both the peaks and steps in the spectra may change their intensity.
In practice, however, a very important approximation is made in the analysis of
angle-dependent spectra: the edge jump is assumed to be constant. The edge jump
has been defined in Sect. 5.4 in conjunction with Fig. 5.20. This procedure allows
one to normalize the angle-dependent resonance intensities to the angle-inde-
pendent edge jump. The theoretical justification of this method lies in the fact
that, at sufficiently high excitation energies above the K-edge, the cross section
becomes atomic-like and therefore angle-independent, on the average. This fact
is often used in the analysis of (S)EXAFS spectra, where the size of the EXAFS
oscillations is normalized to the edge jump [7.7]. From an experimental point of
view this procedures has the advantage that all angle-dependent geometry
effects, e.g., sampling of a different number of chemisorbed species or different
solid angles of detection, see (5.33), are eliminated. Unless otherwise stated we
shall use this procedure in the analysis of angle-dependent spectral intensities
below.
THe size of the edge jump itself contains valuable information, since accord-
ing to (5.33) it is related to the number of absorbing atoms. For the study of
chemisorbed molecules it thus varies with coverage. By normalization to the
incident photon flux, NEXAFS spectra can thus be used to determine surface
coverage. The same analysis procedures apply as in photoemission and Auger
spectroscopy [7.8], with the edge jump taking the place of the intensity of
photoemission and Auger peaks, if the appropriate electron (electron yield
detection) or photon (fluorescence detection) mean free paths are used as
discussed in Chap. 5.

7.1.2 Curve Fitting of Difference Spectra

In many cases it is advantageous to use a simpler analysis method, consisting of
curve fitting difference spectra. Difference spectra are obtained by subtraction of
two original spectra which have been normalized to the same edge jump. This
method is particularly valuable in the analysis of angle-dependent NEXAFS
 7.2 Lineshapes of NEXAFS Resonances 213

spectra. It isolates the angle-dependent resonances by eliminating the isotropic

components of the NEXAFS spectra such as the continuum step.
Although it is not possible to determine the molecular orientation on the
surface from difference spectra alone, as discussed in Sect. 9.8, the analysis of
such spectra provides valuable information on the existence of certain reson-
ances and of their positions and line-shapes. The fit parameters of the resonance
lineshapes may then be used in the fits of the original data, which are, in general,
more complicated but also contain more information. NEXAFS difference
spectra were first used by Arvanitis et al. [7.9J to isolate the 0'* resonances of
chemisorbed hydrocarbons on Cu(100) and to determine their positions.

7.2 Lineshapes of NEXAFS Resonances

This section considers the line shape of the peaks in the near edge spectrum.
The peak-shaped features of primary interest include transitions to antibonding
molecular orbitals in the discrete and in the continuum, Rydberg states, shake-
up states and peaks due to scattering processes involving substrate atoms. We
consider typicallineshapes observed for core excitation resonances, discuss how
to isolate the peaks so that the line shape can be studied, and establish guidelines
for specifying parameters for the description of the peaks. When possible
physical reasons will be given for the observed lineshapes or parameters.

7.2.1 Gaussian, Lorentzian and Voigt Functions

In order to use curve fitting procedures to analyze core excitation spectra,
analytical functions must be used which describe the lineshapes of the peaks. If
the instlAlmental resolution, i.e., the monochromator resolution, dominates, the
peaks will have a Gaussian lineshape, which is given by

(7.1)

where H is the maximum value of the function; r G is the full width at

half maximum (FWHM) of the peak; P is the position of the peak; E is
the in~endent variable, energy; and c is a constant defined by
c = 2~ln 4 = 2.355. In this case the peak is described by three parameters: P,
rG , and H.
The other common lineshape encountered in spectroscopic studies is the
Lorentzian. If the instrumental resolution is small compared to the intrinsic
lifetime-related width of a peak, this lineshape will describe the measured profile.
It is given by

I - H( (E _ P)2
L -
(rd2)2 )
+ (rd2)2 ' (7.2)

where H is the maximum value of the function and rL is the FWHM.

214 7. Analysis of K-Shell Excitation by Curve Fitting

A third lineshape function often encountered is the Voigt profile, represen-

ting the convolution of a Gaussian and a Lorentzian [7.10]. This profile is useful
in cases where instrumental and lifetime widths are comparable. In practice, use
of the exact Voigt profile in curve fitting is time-consuming beause it involves
repeated convolutions, i.e., integrations, and it is therefore more convenient
to use an approximate Voigt line shape, given by the simple addition of a
Lorentzian and a Gaussian. It has been shown that this approximation is of
sufficient quality for most applications [7.11] and the lineshape is given by

Iv = H['1( (E _ P)Z
(r/2f
+ (r /2)Z
) + (1 - '1)e- C»2].
1/Z «E-p)/(n (7.3)

Here '1 is the Lorentzian fraction, and r is the FWHM of the Voigt profile.
Wertheim et al. [7.11] have published graphs that allow the determination of the
component widths r Land r G from the fit parameters '1 and r.
The sharpest and most isolated peaks in K -shell excitation spectra are the
bound state resonances in the form of n* or Rydberg resonances. A particularly
beautiful example is given by the high-resolution spectrum of the N Z molecule
(also see Fig. 4.1), recorded by Chen et al. with synchrotron radiation [7.12],
shown in Fig. 7.1. Here both the vibrational fine structure of the n* resonance
and various Rydberg resonances, merging into the ionization potential, are
shown. In addition, the double excitation feature around 415eV is found to
exhibit detailed fine structure. The dashed lines represent Voigt functions fitted
to the data. The total line width of the narrowest lines is about 130 me V and is
dominated by the Lorentzian lifetime width [7.12,13]. The Gaussian instrumen-
tal fraction is small, 1 - '1 ~ 10%, corresponding to r G ~ 40 me V and
r L ~ 115 me V [7.11].
Figure 7.2 shows examples of fits of n* resonances in lower resolution
spectra, the C=C n* resonance of gaseous C Z H 4 at 284.8 eV [7.14] and the C=C
n* resonance of condensed allyl alcohol (CHz=CHCHzOH) on a Si(111)(7 x 7)
surface at 285.0 eV [7.15]. A Gaussian lineshape provides a reasonable fit to
both peaks whereas a Lorentzian fit is poor because the base of the Lorentzian is
too broad. The reason for these Gaussian line shapes is clear: the intrinsic
lifetime width of these peaks is so narrow that the instrumental resolution
imposes the Gaussian line shape upon the peaks. For the ISEELS spectrum of
C Z H 4 gas in Fig. 7.2 the instrumental resolution was approximately 0.6eV
FWHM [7.14]. This Gaussian contribution dominates over the asymmetry on
account of vibrational excitation detectable in high resolution spectra [7.16-19].
The Gaussian lineshape of the condensed allyl alcohol NEXAFS spectrum
results from the limited resolution (1.1 eV) of the grasshopper monochromator
on beam line 1-1 at the Stanford Synchrotron Radiation Laboratory used to
record the spectrum [7.15].

7.2.2 Asymmetric Gaussian and Lorentzian Lineshapes

Many resonances in core-level excitation spectra are not isolated like the n*
resonances just considered, but overlap with the ionization continuum and/or
 7.2 Lineshapes of NEXAFS Resonances 215

K-Shell Photoabsorption of Gas-Phase N2 • Fig. 7.1

N1s -17tg* la)
N1 s - Rydberg Shape
Series Resonance
Double I
~ Excitations
·iii
I
...cc
r
Q)

c x10
o
.':::
a.
(;
III
.0
<!

(0)4
400 405 410 415 420 Fig. 7.2
Photon Energy (eV)
Ib)
------- Lorentzlon
•
1Te=c
..................... Gaussian

E I
·c IDouble Excitations
:;,
D4,0_0________4~0~2-----4-14----4-1-5----,
~ Id)
1
I:
N1 s - Rydberg Series ~

~
.iii -e
c ~
...c
Q)
~

c
•I:
.!
•
1Te=c
o
.':::
.5
a.
(;
III
.0
<!

406 407 408 409 410 280 290 300 310 320
Photon Energy (eV) Excitation Energy (eV)

Fig. 7.1. (8) High resolution X-ray absorption spectrum of the nitrogen molecule in the gas phase
[7.12]. (b) Vibrational fine structure in the n* resonance, fitted with Voigt profiles shown dashed. (c)
Blow-up of the double excitation feature, revealing vibrational fine structure. (d) Rydberg series
fitted with Voigt profiles, merging into the ionization continuum with a step-like onset at 409.938 eV

Fig.7.2. Fit ofthe C=C n* resonance in the IS EELS spectrum of gaseous C 2 H4 (top) [7.14], and the
same resonance in the NEXAFS spectrum of condensed allyl alcohol (bottom) [7.15]. Both peaks are
fit to Lorentzian (dashed) and Gaussian (dotted) functions which match the height of the experi-
mental peaks (insets show this on an expanded scale). The Gaussian function matches well with the
entire experimental peak, owing to limitations in instrumental resolution, while the Lorentzian fit is
poor because the base is too broad
216 7. Analysis of K-Shell Excitation by Curve Fitting

Cadmium Arachidate/SI(111) Fig. 7.3. NEXAFS spectra of a cadmium ara-

50 chidate monolayer on a Si(lll) surface at 300 K
[7.20]. Shown are spectra with the E vector of
the X-rays orientated parallel to the surface (a)
40 and oriented 20° from the surface normal (b). At
'F the bottom is shown the difference (c) between
c:
:::l these two spectra (solid line) which isolates the
30 three angle-dependent peaks. Superimposed
..ci....
.:(
........ upon (c) is the result (dotted line) of fitting the
20 (a) E difference spectrum using two Gaussian func-
.....>- tions and an asymmetric Gaussian function .
'iii
c: ~ The difference spectrum illustrates the typical
CD
"E 10 increase in peak width and asymmetry with
(b) increasing energy
0

CD 10

-
0
c: 5
CD
.... (c)
CD 0
Ci -5
-10

280 300 320

Photon Energy (eV)

other resonances. In such cases the line shape of the resonances is best examined
by taking difference spectra as discussed in Sect. 7.1.2.
An example of a difference spectrum is shown in Fig. 7.3c, which is the result
of subtracting spectra for cadmium arachidate, a Langmuir-Blodgett (LB) film,
on a Si(lll) surface taken at X-ray incident angles of 90° and 20° [7.20], shown
in Figs. 7.3a and b, respectively. This difference spectrum shows three angle-
dependent peaks, which are isolated from the isotropic components of the
NEXAFS spectra, enabling their lineshape to be easily examined.
One trend which is apparent from such difference spectra as well as the
original core excitation spectra of simple molecules is that the asymmetry of a
resonance and the width increase as the position of the peak increases in energy.
For example, the width of the peaks in the difference spectra for cadmium
arachidate on Si(lll) shown in Fig. 7.3 increase from approximately 1.6eV to
8 eV with increasing energy. The asymmetry also increases with increasing
energy, since the lowest energy peaks are well accounted for by symmetric
Gaussians while the highest energy peak has a quite distinct high-energy tail.
Such effects are also apparent in the original core excitation spectra of other
molecules, independent of whether they are free, condensed or chemically
bonded to a surface. Examples are shown in Fig. 7.4 for the ISEELS spectrum of
gaseous acetonitrile (CH 3 C=N) [7.21], and in Fig. 7.5 for the NEXAFS spec-
trum of condensed propargyl alcohol, HC=CCH 2 0H [7.15]. Note that the
spectra of condensed and chemisorbed CH 3 CN on Ag(llO) are very similar to
 7.2 Lineshapes of NEXAFS Resonances 217

Condensed Propargyl Alcohol NEXAFS

Gaseous CH 3 CN ISEELS

-1[.
Fig. 7.5
Fig. 7.4

c=N

C-H·
a..c-c

...................................... . ........................
......
.., ......
........

280 290 300 310 320 330 280 290 300 31 0 320
Energy Loss (eV) Photon Energy CeV)

Fig. 7.4. Carbon K-edge ISEELS spectrum of gaseous acetonitrile (solid line) [7.21] and fit (dotted
line). This simple spectrum shows the inherent asymmetry of near edge resonance (especially
apparent in the C=N u* rosonance) and the increase in the FWHM of the peaks with increasing
energy. The individual peaks included in the fit are shown with dotted lines. The spectrum is fitted
with an error function step (dashed line) to represent both the free electron continuum and minor
excitonic peaks below the edge. The resultant background step is located 3.8 eV below the actual C
Is ionization energy, labelled IP

Fig.7.S. Carbon K-edge NEXAFS spectrum of condensed propargyl alcohol at 90 K (solid line)
[7.15]. The deconvoluted peaks (dotted lines) illustrate the asymmetry of near edge resonances
(especially apparent in the C=C u* resonance). The spectrum is fit with an error function step (dashed
line) to represent both the free electron continuum and minor excitonic peaks below the edge so that
the resultant background step is located l.5eV below the actual C Is ionization energy. The
continuum step is broader than normal because of differences in the C Is ionization energy of the
various carbon atoms in the molecule

those of the free molecule as shown in Fig. 6.10, and therefore the same fitting
procedures can be applied [7.22].
The increase in width of resonances with increasing energy can be simply
attributed to lifetime broadening. That is, the higher the energy of the final state,
the shorter its lifetime and 'hence the broader the peak. Two mechanisms for the
asymmetry of (1* resonances in the continuum have been discussed. The first
mechanisln involves a combination of lifetime broadening and molecular vibra-
tion along the bond direction [7.23]. As discussed in Sect. 4.3, changes in bond
length result in changes in the position of the (1* resonance [7.24]. As the (1*
resonance moves to higher energy and gets broader its peak height decreases.
218 7. Analysis of K-Shell Excitation by Curve Fitting

Asymmetric Lineshape Fig. 7.6. Explanation for the asymmetry of u*

resonances using a diatomic molecule as an
example. As the internuclear bond vibrates, the
length of the bond changes, which causes shifts
in the position of the resonance. Since the X-ray
absorption process is fast compared to the vi-
brational motion, the NEXAFS spectrum is a
sum of "snapshot" spectra of molecules at differ-
ent stages of their vibrational cycle. The ob-
served resonance is thus the sum of a series of
overlapping peaks (dotted lines) with contribu-
tions from various diatomic bond lengths. We
have assumed that the various peaks have the
save area. Furthermore, the width of these indi-

i-i 11/$",\(,\
vidual peaks varies such that the peaks at lower
energy are narrower than those at higher en-
_ _ _..,r;i~;~·;i~ii;~;~·:·~;·:::···· " ergy, so that the overall resonance (solid line) is
asymmetric with a steep leading edge and broad
Photon Energy (Arb. Units) tail

The sum of these individual resonances, corresponding to "snapshot" NEXAFS

pictures of molecules at different bond lengths during their vibrational cycle, is
therefore asymmetric with a steep leading edge and a high energy tail as
illustrated in Fig. 7.6 (also see Fig. 4.7). The second explanation for the existence
of an asymmetry is provided by scattering theory. As discussed in Sect. 4.2.4, u*
resonances in the continuum can be attributed to pseudo-trapping of the photo-
electron by the [Link] barrier. In this picture the probability ofthe
photoelectron being trapped by the barrier decreases with increasing kinetic
energy, leading to a tailing of the resonance profile toward higher excitation
energies [7.5]. This idea is pursued in more detail in Sect. 7.2.3.
Outka and Stohr [7.4] have proposed a simple asymmetric lineshape func-
tion which was found to provide excellent fits of experimental resonances and
yet is of relatively simple mathematical form. This function is a Gaussian or
Lorentzian function modified so that the width r depends linearly upon energy.
That is, r = E x m + b, where m and b are constants and E is the photon energy
near the resonance. This function makes the Gaussian or Lorentzian peak
asymmetric, but requires four parameters, P, H, m, and b, versus only three for a
symmetric function. It has been found that for the fitting of u* resonances in the
continuum a Gaussian function provides a good approximation, and the two
parameters m and b can be held constant. This reduces the number of unknowns
for this function to only two, thus simplifying the fitting procedure. For example,
all of the peaks except the n* resonances in the carbon K -edge spectra in
Figs. 7.4 and 7.5 were fitted using an asymmetric Gaussian function with width
parameters m = 0.575 and b = -164.75 eV. These parameters are only meaning-
ful for E > 290 eV since for smaller values the width becomes very narrow
( < 2 eV) and is zero for E = 286.5 eV. This function reproduces both the high
 7.2 Lineshapes of NEXAFS Resonances 219

energy tail of these peaks and the greater width of the higher energy peaks. Since
this particular width function approximates the lineshape of carbon K-edge (1*
resonances of single, double and triple bonds, it provides a useful criterion for
deciding whether a particular peak is abnormally broad or narrow. There are
obvious limitations, of course, to the capabilities of the specific parametrization
given above; for example, this function should only be cautiously applied to
resonances in the vicinity or below ~ 290eV. A more flexible use of the
parameters m and b, however, allows one to fit almost all observed NEXAFS
resonance profiles, as discussed in Sect. 7.2.4.
One particularly useful criterion of whether a function provides a meaningful
fit to a peak in a spectrum is whether the function can fit a NEXAFS peak whose
intensity depends upon X-ray incidence angle. That is, assuming that the
location and width of the peak are invariant with X-ray incidence angle, the
same function should fit the peak regardless of X-ray incidence angle with only a
change in the height of the peak. Furthermore, the height of the peak cannot
vary indiscriminately with X-ray incidence angle, but should reflect the orienta-
tion of the bond involved, see Chap. 9.

7.2.3 Giant Resonance Lineshape

Arvanitis et al. [7.5, 25] have introduced a lineshape for the fitting of NEXAFS
continuum resonances which originates from scattering theory, the so-called
giant resonance (GR) lineshape [7.26]. It is given by the scattering cross section
of an electron by a spherical square well potential, which can be obtained in
analytical form [7.27]. This is done by the partial wave method touched upon in
Sect. 2.7 and Appendix A. In practice, the GR lineshape is then given by the
solution for a particular partial wave component (typically I ~ I ~ 3) [7.26]. Let
us define the well radius by a, the depth of the potential well by Vo, and let the
top of the well correspond to a threshold energy Eo. For Eo - Vo < E < Eo we
have a bound state in the well, and an unbound continuum state exists for
E > Eo. For the description of X-ray absorption we take Eo to be the Is
ionization potential and at a photon energy E > Eo the quantity E - Eo
specifies the kinetic energy of the photoelectron above the vacuum level, which
coincides with the top of the well. The cross section for the Ith partial wave
component is then given by the simple formula

(1,
(E) = H
E - Eo
.
SIn v, = E -H Eo I +tantan (),
25: 2 {),
2 . (7.4)

Here (), is the scattering phase shift, and H is an intensity scaling factor. In
particular, for the I = 1 component the phase shift {)1 is given by

kjl (k' a)jo(ka) - k'jl (ka)jo(k' a)

(7.5)
kjl(k'a)j-l(ka) + k'j-2(ka)jo{k'a) '
220 7. Analysis of K-Shell Excitation by Curve Fitting

where the in(x) are spherical Bessel functions of order n given by [7.28]

.() sin x . () sin x cos x

10 x = - - , 11 X =-2----'
x X X

cos x i-2(X) = _ cos2 X _ sin x .

i-l(X) = - - , (7.6)
x x x

The wavevectors k and k' are defined as k 2 = 2m(E - Eo)/h 2 and (k')2 =
2mVo/h2. Similar expressions exist for higher partial wave components
[7.26, 27].
In their analysis of continuum resonances in K -shell excitation spectra,
Arvanitis et al. [7.5] used the I = 1 form of the cross section and associated the
well radius a with the molecular bond length, and the threshold energy Eo with
the Is ionization potential. Figure 7.7 is taken from their work and depicts the
change ofthe scattering profile with the well radius a and depth Vo. The binding
strength of the well is proportional to its volume, a2Vo, and curves (a-e)
represent cases of increasing binding strength. Curve (e) represents the max-
imum cross section possible in this model, and is called the unitary limit. It
corresponds to sin ~I = 1 or ~I = n/2. The resonance maximum is seen to move
closer to threshold as the binding strength increases, and it becomes narrower.
In all cases, the lineshape shows dispersion, i.e., is asymmetric with a finite step-
like component remaining at the high energy side. Note that the onset of the

~
c:
::J 300
.ci
~

~
g 200
:;::;
(J
Q)
rJ)

::! 100
o
o
2 4 6 8 10 12 14
E-EO (eV)

Fig. 7.7. Giant resonance lineshape calculated by means of (7.4) with various values of the well
radius a and the well depth Vo taken from [7.5]. In the model proposed by Arvanitis et aI., a is equal
to the intra-molecular bond length R as indicated in the inset. The curves (a-e) correspond to an
increasing binding strength of the well, characterized by a2 Vo. The curves were calculated with the
following parameters: (a) Vo = 7.6eV, and a = 1.34A, (b) Vo = 8.0eV, and a = l.50A, (c) Vo =
[Link], and a = 1.50 A, (d) Vo = l2.0eV, and a = 1.50 A, and (e) represents the maximum possible
cross section, the unitary limit, and is obtained from (7.4) by setting sin 0 = 1
 7.2 Lineshapes of NEXAFS Resonances 221

peak intensity is always close to Eo, i.e., the intensity does not remain zero over a
significant energy range before it turns on.
The GR lineshape resembles the overall shape of continuum resonances and
it may indeed serve as an appropriate fitting profile, as shown by Arvanitis et al.
[7.5] and Rabus et al. [7.25]. These authors have gone a step further and linked
the parameters describing the GR lineshape with a physical model. The origin of
such a correlation is the muffin-tin picture of the molecular potential of a
diatomic shown in Fig. 2.7. For touching spheres, the radius a ofthe potential
well is equal to the internuclear distance, as is evident from Fig. 2.7 and shown in
Fig. 7.7, and the well depth is given by the inner potential VII = - Vo which is
assumed to be spherically symmetric with respect to the center of the molecule.
In this picture the atomic core parts of the molecular potential are therefore
neglected and the effective scattering potential is taken to be the "inner poten-
tial" well created by the outer sphere.
Despite its apparent success in the curve fitting of a variety of NEXAFS
spectra of free and chemisorbed molecules, there is a problem associated with
the quantitative use ofthe GR lineshape as proposed by Arvanitis et al. [7.5,25].
The problem arises from the fact that in the central molecular reference frame
the photoelectron wave is typically not of I = 1 partial wave character. This
partial wave only describes the photoelectron in the central atomic potential of
the excited atom as discussed in Sect. 2.7 and Appendix A. Rather, in the
molecular potential centered at the center of gravity of the molecule the
photoelectron wavefunction will, in general, contain many partial wave com-
ponents. Furthermore, in the well-studied case of the N2 molecule, the resonant
partial wave in this reference frame corresponds to the 1= 3 partial wave
component [7.29]. It therefore appears that the correlation between the well
radius and the molecular bond length is somewhat fortuitous.

7.2.4 Giant Resonance Versus Asymmetric Gaussian Lineshapes

The giant resonance, asymmetric Gaussian, or Lorentzian lineshape may be
used to account for the asymmetric shape of continuum resonances. This is
illustrated in Fig. 7.8 by curve fits of the spectrum for gas phase N 2. Here the
emphasis is on the fit of the CT* resonance near 419 eV. The Rydberg resonances
below the IP (409.9 eV) and the multielectron structure near 415 eV were simply
accounted for by suitable symmetric Gaussians and an error function step at the
IP was introduced to mimic a smooth atomic-like background. For the fit ofthe
CT* resonance in Fig. 7.8a we have used a GR lineshape function (solid line) with
the parameters Eo = 414.5eV, a = 1.1 A, and Vo = 21.3eV, similar to the one
used by Wenzel et al. [7.31, 32] for N2 on Fe(111). In Fig. 7.8b the GR lineshape
function has been replaced by an asymmetric Gaussian function with para-
meters P = 419.2eV, m = 1.11, and b = -459.8eV. There is little difference
between the two fits and we conclude that either function can account for the
large asymmetry in the experimental lineshape of the CT* resonance.
222 7. Analysis of K-Shell Excitation by Curve Fitting

Nitrogen Gas Fig. [Link], b. Curve fits of the gas phase

N2 ISEELS spectrum [7.30] employ-
(a) • Giant Resonance ing different lineshapes to account for
the a* resonance. (a) Giant resonance
Line Shape
lineshape function with parameters Eo
= 414.5eV, a = 1.1 A, and Vo
=21.3eV. (b) Asymmetric Gaussian
function with parameters P
= 419.2eV, m = 1.11, and b =
- 459.8 eV. The Rydberg resonances
between 405eV and 410eV and the
multielectron structure near 415 eV
2' were accounted for by symmetric
c: Gaussians. An error function step was
::::l
used at the 409.9 eV IP
.0
....
ro
(b) Asymmetric Gaussian
>-
:!::
C/)
Line Shape
c:
OJ
C

395 405 415 425 435 445 455

Excitation Energy (eV)

For the asymmetric line shape function the parameter P characterizes the
peak position. For the GR line shape function the parameter Eo defines a
"threshold energy". The determined value of Eo = 414.5eV does not agree with
the 409.9 eV value for the IP. This indicates a problem with respect to the
physical meaning of the GR lineshape parameters as indicated in Sect. 7.2.3 on
purely theoretical grounds. Hence, although the GR line shape function can well
account for the shape of continuum resonances it may be dangerous to link the
derived parameters to physical parameters like the IP or the bond length.

7.3 Lineshapes of NEXAFS Steps

7.3.1 Origin of Steps

In addition to peaks, near edge spectra contain one or more step-like features
referred to as continuum steps. These steps are the result of excitation of the
 7.3 Lineshapes of NEXAFS Steps 223

core electron to a continuum or quasi-continuum of final states, e.g., to the

smooth density of states. Steps are difficult to examine experimentally, because
they are almost always obscured by other spectral features. In particular, the
position and shape of the edge are difficult to discern from experiment, as is
evident from Fig. 7.1d where the density of Rydberg resonances becomes so
high that a continuum-like smooth cross section is observed well below the
accurately known ionization potential at 409.938 eV [7.12], where the con-
tinuum step is located. This section will emphasize the importance of these
structures in analyzing core-excitation spectra, illustrate approaches to model-
ling them, and present generalizations regarding their characteristics.
There are several types of continuum steps which can be observed in core-
level excitation spectra. The first type which appears most prominently in gas
phase spectra falls at the IP and is due to transitions to the continuum of free
electron final states, as already discussed for N2 in conjunction with Fig. 7.1.
Above the IP, additional (smaller) steps may exist due to multielectron excita-
tion thresholds, as revealed by the spectrum of argon gas in Fig. 4.8. Continuum
steps also occur in solids. In insulators, the lowest unoccupied states lie above
the band gap, and in these cases the step corresponds to transitions to the
conduction band minimum as discussed theoretically by Elliott [7.33]. In
conductors the lowest energy unfilled states lie above the Fermi level and the
absorption edge in metals corresponds to transitions to such conduction band
states. The intensity modulations above the edge are characteristic of the
appropriate partial wave projection (l = 1 for K-shell excitation) of the empty
density of states [7.34]. In addition to the step at the IP, observed for free
molecules, molecules adsorbed on metallic surfaces may also exhibit a lower-
energy step corresponding to transitions to metal states above the Fermi level.
The empty metal density of states forms a continuum which may hybridize with
molecular states exhibiting a step-like feature in the core excitation spectrum.
Several examples of such steps will be discussed below. Despite the problem that
the continuum step is usually obscured, it is quite important to be able to
account for it while analyzing core excitation spectra because it can strongly
affect the position and area of peaks in its proximity. Below we shall discuss how
such steps can be accounted for by curve fitting.

7.3.2 Gaussian and Lorentzian Shaped Steps

The most common approach to mathematically model the continuum step is
that used by Parratt,
shown in Fig. 2.1 for the K-shell spectrum of argon gas.
Here it is assumed that the lineshape of the continuum step is determined by the
lifetime of the core hole. This implies the convolution of a square step with a
Lorentzian, i.e., an integral of a Lorentzian function, which yields an arctan
function,

[step = H[ "21 +;1 arctan (E-P)]

r L /2 . (7.7)
224 7. Analysis of K-Shell Excitation by Curve Fitting

Here P is the position of the inflection point of the step; H is the step height of
the function; r L is the width of the step; and E is the independent variable,
energy. This approach has also been used in fitting the X-ray absorption spectra
for Pt and Ir compounds [7.2] and in the analysis of the C(ls) edge region of
diamond in a high-resolution study of excitonic effects [7.3], see Sect. 7.4.2.
If, on the other hand, we assume that the intrinsic lineshape of the con-
tinuum step is quite narrow «0.5 eV) and the instrumental resolution is worse
than this (;;:: 1.0eV), then the lineshape ofthe continuum step will be convoluted
with a Gaussian function. If we make the simplification that the intrinsic shape
of the continuum step is square rather than Lorentzian-derived, then the
resolution limited continuum step is simply this square step convoluted with a
Gaussian. This yields a formula for the continuum step based upon the so-called
error function (erf) which is commonly available in mathematical tables [7.28].
The functional form of an error function step is

[step = H[~ + ~erf(:G/C:) l (7.8)

where P is the position of the inflection point of the step; H is the height of
the function immediately above the step: r G is the FWHM of the step, and
c* = 2JiD2 = c/ = 1.665. J2
The arctan and the error functions are compared in Fig. 7.9 together with the
corresponding Lorentzian and Gaussian functions. In all cases we have assumed
r L = rG = 1 eV and have normalized the maximum intensity to unity. Note that
the arctan and error functions are simply the integral of the Lorentzian and
Gaussian functions, respectively (renormalized to unit intensity). Both step

Gaussian and Lorentzian Profiles and Steps

1.0

0.9
-Gaussian
---- Lorentzian -_ .. -
-= 0.8 Fig. 7.9. Comparison of arctan
'-e"" 0.7 and error function steps. The
arctan step (dashed) is based
~ 0.6
upon the integral of a Loren-
.~ 0.5 tzian peak (dashed) and its
1:
FWHM is related to the lifetime
~ 0.4
\
\
\ of an excited state. The error
\
~ 0.3 \
\ function step (solid) is based
~ 0.2 \, upon the integral of a Gaussian
0.1
' .........
-- ............ - peak (also solid) and the
FWHM of the step is related to
o the instrumental resolution. We
-2.0 -1.5 -1.0 -0.5 0 0.5 1.0 1.5 2.0 have assumed a FWHM r G
Energy. E-P (eV) = rL = leV in all cases
 7.4 Examples of Steps 225

profiles require three parameters to describe them: the position of the inflection
point of the step, the FWHM of the rise, and the height of the step.
With spectra of moderate resolution (~ 1 eV) it would be difficult on the
basis of the actual fit to the spectra to prefer one function over the other, since
merely decreasing the width of the arctan step makes it look like the error
function step. The advantage of the error function, however, is that the para-
meter describing the width is related to a known quantity - the instrumental
resolution. In contrast, the width parameter of the arctan function is related to
the lifetime of some excited state which is not a priori known. Thus an advantage
of the error function step is that, if the assumption of limited resolution is valid,
there are only two unknown parameters needed when fitting: position and
height.
A second complication to modelling the continuum step is that the steps are
usually not constant above the edge but exhibit a decay due to decreased
overlap between the initial and final states in the electronic transition. This is
apparent and was included in the modelling of the core excitation spectra of
acetonitrile (Fig. 7.4) and propargyl alcohol (Fig. 7.5). To model this decline the
step functions given by (7.7) and (7.8) may be multiplied by an exponential
decay:

E~p+r, (7.9a)
r step
xp -
-
I
step e -d(E-P- r) , E >p+ r, (7.9b)

where P is the position of the inflection point of the step, r is the width of the
step, d is the exponential decay coefficient, and E is the independent variable,
energy. Note that the decay is turned on slightly above the step to avoid
distorting the shape of the edge region. Also, the curvature of the decay in many
spectra, e.g., those of acetonitrile and propargyl alcohol shown in Figs. 7.4 and
7.5, is so small that a linear decay rather than an exponential one provides a
reasonable fit, as well.

7.4 Examples of Steps

7.4.1 Continuum Steps for Free Molecules

To show that the error function provides a reasonable first approximation to the
continuum step, we will demonstrate its use in the fitting of several gas phase
ISEELS spectra. The gas phase provides a good starting point because the
inflection point of the step coincides with the core electron ionization energy of
the atom involved. There may be more than one of these continuum steps in the
spectrum of a molecule that contains the same atom in different chemical
environments, i.e., C-C versus C-O bonds. This is equivalent to chemical shifts
observed in photoemission.
226 7. Analysis of K-Shell Excitation by Curve Fitting

Fig. 7.10. Carbon K-edge ISEELS

spectrum of gaseous ethylene (solid
line) [7.14] and a fit to the spectrum
(dotted line). The spectrum is fit such
that the inflection point of the con-
234567 tinuum step is located at the position of

fV"~ the C Is ionization energy. All peaks

r!-------------- apparent in the spectrum including the

small Rydberg peaks near the ioniza-
l: tion limit have been included in the fit
(dotted lines) as separate peaks. Over-

;:
~
f :\.' ", .... .....
all, the fit is satisfactory except right
near the ionization limit (see inset)
:: I···· ....., .....•:: .....

.•L":.. ~ ':<...::~.~ " . . :.<. where individual Rydberg peaks are

not resolved and the limitations of the
288292296300304 error function (dashed line) to represent

~
the continuum step become apparent.
The major peaks in the spectrum can
be assigned. Peak 1 is the C=C n*
resonance, peaks 2 and 3 are attributed
to C-H* /Rydberg resonances, peaks

___--<.J~/1~.·. : ~· ·_ ___'=_ _ __
4-6 are multielectron peaks, and peak
7 is the C=C a* resonance

280 300 320

Energy Loss (eV)

Figure 7.10 illustrates some of the difficulties encountered in fitting an

appropriate step function. For ethylene gas the shown ISEELS spectrum [7.14]
can be fit with an error function step whose inflection point is located at the C Is
ionization energy of 290.8 eV [7.35]. The first problem arises from the numerous
small peaks near the ionization threshold due to Rydberg and other minor
excitations, which obscure the precise position and shape of the continuum step.
As shown in the fit it is possible to include a discrete peak in the least squares fit
for each apparent peak in the spectrum (peaks labelled 1-6 are Gaussians and
the peak labelled 7 is an asymmetric Gaussian function) and thereby obtain a
reasonable approximation to the measured spectrum, except at the precise
position of the step where small deviations are still apparent. The reason for the
deviations near the ionization energy lies in the complicated nature of the
RydbergjC-H* resonances as seen more clearly in the high resolution spectrum
in Fig. 6.3. This structure is not approximated well by a single Gaussian
function. In addition, the deviations near the ionization energy may also be the
result of limitations of the error function in approximating the true shape of the
continuum step. Nevertheless, the error function step appears to provide a good
background above the edge, particularly near the C=C (1* resonance (labelled 7)
which is of special interest in the study of the orientation and bonding of
ethylene.
 7.4 Examples of Steps 227

Since pure Rydberg peaks close to the continuum step are of only limited
interest in studies of molecular orientation and bonding, they could be ignored
and the fitting procedure greatly simplified by treating them in combination
with the continuum step as a background which is approximated altogether by a
single error or arctan function. For example, in the N2 spectrum shown in Fig.
7.1 it is apparent that lowering the step position by about 0.5 eV would well
account for the intensity of the highest energy Rydberg transitions. In general,
depending on the instrumental resolution and other factors, the position of this
effective background step will be shifted to lower energy by up to 4eV from the
true ionization energy. This approach was used for the ISEELS spectrum of
gaseous acetonitrile shown in Fig. 7.4. In this case the positions of the Rydberg
peaks are not apparent as in the case of ethylene so it would be somewhat
ambiguous to include them individually in the fit. Instead a single error function
step is used to model the background resulting from both the continuum step to

Nitrogen Gas CO Gas

Z:
'iii
c
Q)

405 415 425 435 445 455

Excitation Energy (eV)

Fig. 7.11. Curve fits of the gas phase ISEELS spectra [7.30] of N 2 and CO (C K-edge) by use of one
or two step functions. Note that the 1[* resonance has been omitted from the shown spectra. The
lowest energy step is at the IP ([Link] for N2 and 296.2eV for CO). The second step, shown dotted,
is located near 416eV and 301 eV, respectively, and falls just above the multielectron peaks. It is
attributed to multielectron transitions. Symmetric Gaussians were used for the Rydberg and
multielectron peaks and asymmetric Gaussians for the (J* resonance. The fit in Fig. [Link] is the same
as in Fig. [Link]
228 7. Analysis of K-Shell Excitation by Curve Fitting

free electron states and the Rydberg excitations. The step is positioned at
[Link], which is 3.8eV below the actual C 1s ionization energy of 292.68eV
[7.35]. Naturally, the simplification inherent in using a single step function to
represent the background resulting from both the continuum step and Rydberg
excitations implies that the spectral region between the inflection point of the
fitted step and the actual ionization limit has to be cautiously interpreted.
A second kind of step may arise from multielectron (ME) shake-off effects at
energies above the core ionization potential. An example is shown in Fig. 4.8 for
argon gas, where a sizeable second step is observable about 20eV above the IP.
Such steps may exist at the various double ionization energies, corresponding to
simultaneous ionization of a core and a valence electron, and are often preceded
by shake-up peaks involving secondary valence-Rydberg and valence-valence
processes. Figure 7.11 indicates the presence of sizeable ME steps in the K -shell
excitation spectra of N2 and CO (C K-edge). Here we compare spectra curve-
fitted with just one step at the one-electron IP to a curve fit that includes another
step above the well-studied ME features near 415 eV (N 2) and 300eV (CO). Note
the close relationship between the N2 and CO spectra which arises from the
isoelectronic nature of the two molecules. The second step, shown dotted, leads
to an improvement in the overall fit and to a more realistic line shape of the u*
resonance. We shall see in Sect. 7.4.3 that the second step is crucial for the
quantitative analysis of the NEXAFS spectra of N2 on Fe(111).
Close inspection of the K-shell spectra of CO in Fig. 4.5 also reveals weak
features above the u* resonances in both the carbon (~309 eV) and oxygen
(~555eV) spectra which can be attributed to ME processes. Also, in the same
figure, the C K-shell spectrum ofH 2CO shows similar structures around 54geV.
It appears, however, that in molecules such multielectron peaks and steps
decrease in intensity with increasing separation from the one-electron IP, and in
many cases are weak compared to the one-electron excitation features.

7.4.2 Continuum Steps for Condensed Molecules, Polymers, and Solids

For bulk samples the same approach can be used to model the continuum step
and excitonic states near the edge. For molecular solids the Rydberg peaks are
often not as apparent as in the gas phase spectra because the large spatial extent
of the Rydberg orbitals causes orbital overlap with concomitant lifetime broad-
ening. The use of the error function for the fit of the spectrum of a condensed
molecule (propargyl alcohol) is shown in Fig. 7.5. The spectrum can be fit with
an error function step located at 289.7 eV, which is 1.5 eV lower than the
estimated C 1s binding energy of 291.2 eV because the broadened Rydberg
states are also accounted for by the step function. Also, for condensed molecules
the continuum step is not expected to occur at the gas phase IP due to the
presence of extra-molecular relation effects in the solid. Such extra-molecular
screening effects of the core hole, caused by the finite polarizability of the
surrounding matrix, are expected to be of the order of 1-2eV [7.36].
 7.4 Examples of Steps 229

In solids with long range periodicity, absorption steps are also observed.
Here the steps correspond to transitions to the lowest unfilled energy bands
above the conduction band minimum. For insulators and semiconductors th,e'
absorption step may be modified in shape and energy by excitonic effects and
the presence of states in the band gap. A beautiful example of an exciton is
encountered in the high resolution X-ray absorption spectrum of diamond
recorded by Morar et al. [7.3] shown in Fig. 7.12. The step-like onset of
conduction band states is preceded by a sharp exciton, similar to the Rydberg
resonances that precede the step in gas phase spectra. If this spectrum were
modelled with one step to represent the combination of the continuum step and
the excitonic states near it, the position of the step would be below the C Is
ionization energy by 0.19 eV. It should be noted that the fit in Fig. 7.12 involves
a theory of Elliott [7.33] which properly accounts for the dielectric response of
the medium to the core hole close to threshold. A case related to diamond is that
of an unsaturated polymer with a band gap. Here the step is preceded by a

1.4 '---"---""T"---,.--r--.,---....,
(a)

1.2 Diamond C K-edge

1.0

0.8

i' 0.6
x
!l 0.4
c
:0
o
£ 0.2
'0
Qj
>=
.. 0.0 '--_-'-_--'--_----L_ _'-_-'-_--1
t: 280 290 300 310 320 330 340
8!.c 1.2 ,-----,_--,._--,._~----,..----,..-....,
g (b)

" 1.0
m
.
~
'0
Discrete Excitonic
States
--........
5 0.8
"
en" I
I!
0.6
I·
~ Fig. 7.12. (a). High resolution X-ray absorption
0.4
1 spectrum of diamond and comparison to the
'I
II
calculated band density of states [7.3]. (b)
Blow-up of the threshold region and decon-
0.2 I\ volution by curve fitting, revealing a pronoun-
\ ced exciton located 0.19 eV below the step-like
0.0 L~~~~~-'--.:..:-::i:...:-:....:-J:....:-::..:-:i:..:-:J onset of transitions to states above the
286 287 288 289 290 291 292 293 conduction band minimum [7.3]. The curve fit
Photon Energy (eV) involved a theory by Elliott [7.33]
230 7. Analysis of K-Shell Excitation by Curve Fitting

C-H* /Rydberg resonance as discussed in Sect. 6.4.3 and shown in Fig. 6.20 for
polyethylene and Langmuir-Blodgett films [7.20].
States in the band gap have been observed by Ritsko [7.37] for highly doped
polyacetylene, and by Fink et al. [7.38, 39] for various conducting polymers.
Results for polyacetylene are shown in Fig. 7.13. The IS EELS spectrum of
undoped polyacetylene reveals a pronounced n* resonance which disappears
upon doping. Instead, a much weaker lower energy structure appears, arising
from doping-induced states in the gap. It is interesting to note that Ritsko

Poly acetylene
,,
C K-shell .-"\\
,,
\
\
\
I \

+ \
------ undoped I •
'" - - saturation
1 Fig. 7.13. ISEELS K-shell excitation
~ ~x­
::> doped (AsF 5 1 I' ' '\ / 20 spectrum of undoped polyacetylene
~
I \
I \ (filled circles, dashed line) and poly-
10°0 ~
acetylene doped to saturation with
§ AsF 5 (open circles, solid line) [7.37].
c Upon doping the pronounced n* res-
o 00
o onance with a maximum at 284.1 eV
disappears (note intensity decrease by
o 0
factor of 20) and the leading edge shifts
o to lower energy by 1.2 eV. The intensity
-3 -2 -1 0 2 3 at negative relative energy is attributed
Relative Energy (eVI to states in the gap

Polystyrene NEXAFS

Fig. 7.14. Carbon K-edge NEXAFS spectrum

of polystyrene at 300 K (solid line) and fit (dotted
line). Overall, the spectrum can be deconvoluted
like the spectrum of any gas phase or condensed
molecule. The spectrum is fit using an error
function step (dashed line) located below the C
Is ionization energy and using typical Gaussian
and asymmetric Gaussian lineshapes (dotted
lines). The labelled references are assigned by
comparison to the ISEELS spectrum of benzene
[7.40]. The first continuum shape resonance
labelled a;1 is more intense than that in the
benzene spectrum because it also has a contri-
280 290 300 310 320 bution from the C-C single bonds of the linking
Photon Energy (eY) chains
 7.4 Examples of Steps 231

attributed the n* resonance to an "exciton". Our reinterpretation of his spec-

trum has an important consequence. Since the n* resonance disappears upon
doping, the spectrum suggests a rehybridization of the C-C bonds in poly-
acetylene with doping, changing from alternating single and double bonds in
undoped polyacetylene to a chain of single bonds for the doped sample.
A fit of the K -shell spectrum of another polymer, polystyrene, is shown in
Fig. 7.14. This spectrum consists of several discrete peaks, which can be assigned
to specific final state resonances based upon the assignment of benzene [7.40],
and to a single background step at 289.9 eV. The background step is positioned
slightly below (about O.4eV) the vacuum-referenced C Is binding energies of
benzene [7.35] and long chain hydrocarbons [7.41]. Overall, the spectrum
strongly resembles the spectrum of benzene which is a large component of the
polymer.

7.4.3 Steps for Physisorbed and Chemisorbed Molecules

The NEXAFS spectra of molecules adsorbed on surfaces present the largest

challenge for curve fitting. In principle, several steps can exist. Similar to the gas
phase a step may be found at the ionization potential, the energy necessary to
excite a is electron to the vacuum level (VL). We shall refer to this step as the VL
step. Due to relaxation effects the VL step is expected to be lower in adsorbed
molecules than in free molecules. In addition, a step may occur due to trans-
itions to the densely spaced unfilled electronic states of the metal above the
Fermi level (FL), if such states have a finite projection on the molecule, i.e., mix
with moleqdar states. The inflection point of the step should be precisely located
at the core level excitation energy measured relative to the FL and is therefore
called a FL step. For molecules adsorbed on metallic surfaces, photoemission
binding energies are typically referenced to the FL and therefore correspond to
the position of the FL step. The difference in energy between the two steps is
given by the work function.
An intriguing question is whether the FL step, if present, is the lowest energy
structure in the NEXAFS spectrum of a molecule, e.g., lies below the n*
resonance in unsaturated molecules. At first sight one would expect this to be
true since by definition all states below the FL of the metal are filled in the
ground state and therefore no empty final states are available below the FL. This
argument is incorrect, however, the reason being that transition energies are
determined by final state effects, not the ground state properties. The core
electron binding energy relative to the FL of an atom or molecule bonded to the
surface depends on the amount of core hole screening by the metallic electrons.
In the photoemission case the molecule is ionized, and the photoelectron itself
does not contribute to the screening of the core hole. The n* resonance energy,
on the other hand, is determined by intra-molecular screening, i.e., self-screening
of the core hole by the excited electron in the n* orbital. This latter energy is
almost identical for free and chemisorbed molecules because the molecule
232 7. Analysis of K-Shell Excitation by Curve Fitting

remains neutral during the bound state excitation and therefore core hole
screening by metal electrons is small or non-existent.
From this picture it is apparent that, in principle, the n* resonance energy
can be lower than the FL step, i.e., if the self-screening is more effective than the
metal screening. Indeed, this has been observed for the 0 K -edge excitation for
CO on Cu(100) [7.42] and also for physisorbed and chemisorbed O 2 on Pt(111)
[7.43]. This latter, particularly beautiful example, is shown in Fig. 7.15. Here the
Fermi level and vacuum level steps are shown shaded and dashed and the
respective positions are indicated. Clearly, the n* peak position falls below the
Fermi level step as determined by XPS [7.44]. As expected, the Fermi level step
is lower in energy for chemisorbed O 2 than for physisorbed O 2 , owing to the
stronger interaction with the surface and the resultant enhancement in screening
of the core hole on the molecule by the metallic electrons. On the other hand, the
n* resonance positions are nearly identical.

Fermi and Vacuum Level Steps

(a)

Physisorbed 0 2
on Pt(111)
Fig. 7.15. NEXAFS spectra for O 2 (a) physisor-
bed, and (b) chemisorbed on Pt(1tt) [7.43] and
curve fits. Steps at the XPS binding energies
[7.44] relative to the Fermi level (FL) and
vacuum level (VL) are shown shaded and dot-
ted, respectively. The FL steps fall at 535.8eV
for physisorbed and 531.0eV for chemisorbed
02 ' The VL steps are higher in energy by the
«I
6.t eV work function. The figure illustrates that
t
«I the n* resonance falls below the FL steps in
c..
both cases. For the curve fits the dashed steps at
the position of the nO resonances were used
instead of the FL steps. For the physisorbed O 2
spectrum this was necessary to account for the
finite intensity between 533eV and 536eV, as
525 530 535 540 545 550 555 discussed in the text in conjunction with Fig.
Photon Energy (eV) 7.18

The presence and height of a Fermi level step is expected to follow Fermi's
Golden Rule, where the final state density is the appropriate partial wave
projection of the conduction band onto the molecule. This rule suggests several
guidelines as to the presence and intensity of a FL step in the NEXAFS
spectrum of an adsorbed molecule on a metal surface. These are: (1) Fermi level
steps will be more intense for strongly adsorbed molecules than for weakly
adsorbed (e.g., physisorbed) molecules, for which they may be absent altogether.
 7.4 Examples of Steps 233

(2) For K-shell excitation the height of the Fermi level step depends on the p-like
density of states and symmetry of electronic energy levels near the Fermi level in
both the adsorbate and the metal surface. That is, the greater the number of
adsorbate energy levels near the Fermi level of the metal and the smaller the
energy difference between the levels of the metal and the adsorbate which are
symmetry-allowed to interact, the greater the height of the Fermi level step. (3)
Because of core hole localization, the height of a Fermi level step at different K-
edges in heteroatomic molecules depends upon the adsorbate geometry relative
to the substrate. The spectra of adsorbate atoms near the surface will exhibit
more intense Fermi level steps than atoms farther away.
Several examples of Fermi level steps in the NEXAFS spectra of various
adsorption systems have now been observed which support these generaliz-
ations. For example, the system of O 2 adsorbed on Ag( 11 0) represents a case of a
molecule which interacts strongly with the metal and is characterized by an
orientation of the 0-0 axis parallel to the surface and a significant stretching of
the 0-0 bond [7.45]. Thus the requirement of good overlap between the
adsorbate and metal electronic states is met. In addition, the 0-0 (}"* MO has a
relatively small energy separation from the Fermi level. The Fermi level step is
therefore expected to be strong and indeed it is the only continuum step
apparent in the spectrum, as shown in Fig. 7.16. Because of the azimuthal and
polar ordering of the molecule on the surface, the 0-0 (}"* resonance is

02/Ag(110) NEXAFS

9=
[110] 90

10
Fig. 7.16. NEXAFS spectrum of O 2 on
Ag(llO) for E along [1 TO] and normal and
grazing X-ray incidence angles. Note that
there is only one step (dashed line) in the
spectra which coincides with the XPS
520 530 540 550 560 binding energy relative to the Fermi level,
Photon Energy (eV) marked FL, at 529.3eV [7.45]
234 7. Analysis of K-Shell Excitation by Curve Fitting

minimized under certain angles of X-ray incidence, thus allowing the Fermi level
step to be easily observed, as in the lower spectrum in Fig. 7.16.
In contrast, the requirement that there be a match between the energies of
the electronic levels of the adsorbate and of the metal usually implies that the
step, although strong, is obscured by other resonances in the near edge spec-
trum. For example, in the NEXAFS spectrum for CO adsorbed on Mo(llO)
[7.4, 46], shown in Fig. 5.23, the onset of a Fermi level step is just discernible at
the position of the C Is binding energy (285.0eV) [7.47] as a shoulder on the low
energy side of the C=O n* resonance. Note that for carbon K-shell NEXAFS
spectra structures in the transmission function of soft X-ray monochromators
can masquerade as a Fermi level step. In the case of CO on Mo(llO) the overall
good normalization (as indicated by, for example the flatness of the pre-edge
region) and comparison of the raw detector signals from the sample and the
reference monitor (Fig. 5.23) indicate that the observed structure is not a
monochromator artifact but an actual Fermi level step.
Most hydrocarbons are rather weakly adsorbed on the noble metal silver,
and therefore the primary step observed in their K-shell spectra is found to
occur at the VL. This has been investigated in a series of studies by Solomon et al.
[7.48-50], and Fig. 7.17 shows some of their results. Here C K-edge spectra and
curve fits of ethylene, 2,5-dihydrofuran (DHF) and benzene on Ag(110) are
shown. It is apparent from the polarization dependence of the spectra that all
molecules lie down and are n-bonded to the surface. The position of a possible
FL step, determined by XPS, is shown in all cases. It is clear that especially the
normal incidence spectra cannot be fit with a single FL step. Hence, the spectra
were curve-fit using a VL step, located at an energy which is given by the XPS
binding energy plus the work function. The work function 4.5 eV of the clean
Ag(llO) surface was chosen. Such a step can account for all spectra, except for
the dashed areas in the grazing incidence spectra. This discrepancy indicates
that there may in fact be a finite FL step due to n-like metal states which have
mixed with n* molecular states, as expected from the n-bonding configuration of
the three molecules and from the proximity of the n* orbital and the Fermi level.
The FL step would be preferentially visible at grazing incidence when the E
vector orientation emphasizes transitions to states of n symmetry. Thus a better
fit of the grazing incidence spectra would involve a first step at the FL position, a
reduced intensity of the first two resonances (n* and/or C-H*) and a second VL
step.
There is another interesting explanation for an energy step below the VL in
Fig. 7.17. The idea for this novel type of step comes from the spectrum of
physisorbed O 2 on Pt(111) shown in Fig. 7.15. It is clearly seen that there is a
finite intensity in that spectrum between the n* resonance and the FL step, i.e., in
the region 533-536 eV. In the fit of the spectrum shown in Fig. 7.15 this intensity
is accounted for by a step which lies at the peak position of the n* resonance. A
similar step is also indicated in the spectrum of chemisorbed O 2 in that figure. A
possible physical model for this step is suggested by Fig. 7.18, where the K-shell
spectra of O 2 in four different phases are compared: (a) gas phase [7.51], (b) a 9-
 Ethylene/Ag (110) 2,5-DHF Submonolayer/Ag (110) 8enzene Submonolayer/Ag (110)

H,C=C. ..H I ,
1I'*c=c. C-H* 11'*1 \
1I'*c=c H' 'H ... ....I
Q g'-_'
a*c-c,c-O
I~
en 11'*2
.~ 4~
[Link] C-H* ~
::J

~
cu
a*1 a*2
..
E
......
:0 a*c=c E
...cu +~
...> ~. ~........-
';;; I~I...J!J.·:'·I""·· I
lii~-+
...
[Link]

·__~~:':':'~~~·:::~~::~~':':':.!.!~~l""" ••• ____ •

IVL FLI
x.'t·:2:. I.: :; ~: .: ; ; ;: : : : :
IVL ....:.0-
275 285 295 305 315 275 285 295 305 315 275 285 295 305 315 325 m
><
I>l
Photon Energy (eV) 3
'5!..
Fig. 7.17. Carbon K-shell NEXAFS spectra of ethylene [7.49], 2,5-dihydro- step at the FL position alone. In order to account for the shaded areas, not
"'"
s..
f;IJ
furan (DHF) [7.50], and benzene [7.48] on Ag(llO) as a function of X-ray accounted for by the shown curve fits, a lower energy FL step or a ME step as
incidence, and curve fits. All curve fits used a step at the vacuum level (VL) discussed in conjunction with Fig. 7.18 would have to be included. The XPS ~
position, shown dashed~otted, determined from the XPS binding energies binding energies relative to the FL are 285.0eV for ethylene [7.49], [Link] for
relative to the Fermi level (FL) plus the work function of 4.5 eV for the clean 2,5-DHF [7.50], and 284.7 eV for benzene [7.48]
IV
Ag(llO) surface. Note that the normal incidence spectra cannot be fit with a t.H
V.
236 7. Analysis of K-Shell Excitation by Curve Fitting

3.5 Fig. 7.1S. K-shell absorption spectra for the

(a) O 2 molecule (a) in the gas phase (high resolu-
2.8
2.1 tion) [7.51], (b) a 9-layer condensed film at
17K on Pt(111), (c) a physisorbed monolayer
1.4
on Pt(111) at 17 K, and (d) a chemisorbed
0.7 monolayer on Pt(111) produced by annealing
0 to 80 K [7.43]. Note the appearance of a low-
10 (b)
energy step for O 2 adsorbed on Pt(I11) which
8 increases from the thin multilayer to the chem-
6 isorbed layer. This step is proposed to be
~
r:: 4 9 Layers caused by multielectron excitations involving
::J °2/Pt (111 ) Is -+ n* excitation coupled with conduction
2
£ electron excitations across the Fermi level in
.e 0
0.8 (e) the substrate. This step turns on as the integral
~ of the n* peak shape and its intensity is pro-
·00 0.6
r:: portional to the n* interaction with the surface
Ql
C 0.4
0.2
0
0.6

0.4

0.2

O~~~~LW~~LU~LU~~
525 530 535 540 545 550 555
Photon Energy (eV)

layer condensed film on Pt(111), (c) a physisorbed monolayer (17 K), and (d) a
chemisorbed monolayer (80 K anneal) [7.43]. In the gas phase spectrum the
intensity drops to zero between the n* resonance and the a* resonances, while it
gradually increases between the thin multilayer and the chemisorbed monolayer
spectra, as indicated by the shaded step function. Spectra of O 2 on Pt(111) in
different phases recorded at grazing incidence, not shown in Fig. 7.18, show
identical behavior. The situation for the physisorbed layer is most revealing
since there are no molecular states in the region between the n* resonance and
the FL step at 535.8 eV and by definition all metal states below the FL are filled.
Hence no one-electron transitions are allowed in this energy region.
This points to a multielectron (ME) nature of the intensity in question. One
such mechanism consists of K -shell excitations to the n* orbital coupled with
valence electron excitations across the Fermi level in the substrate. The coupling
of the molecule to the valence states of the metal is caused by the back bonding
metal-n* interaction. In the strong coupling limit, the interaction of a n* orbital
with the electronic states of the substrate leads to a splitting of the n* orbital into
filled and empty "n*" states, which in the presence of a core hole fall just below
and just above the Fermi level, respectively [7.52]. Therefore the ME process
would gradually turn on with the primary n* resonance itself and would be
 7.4 Examples of Steps 237

enhanced with increasing coupling to the substrate. This is consistent with the
larger step observed for the stronger-coupled chemisorbed O 2 relative to
physisorbed O 2 , In the thin multilayer spectrum only the bottom layer couples
to the substrate and the effect is expected to be reduced, as observed. Mathemat-
ically, the turn-on of such a ME step would be well described by a lineshape that
is the integral of the n* resonance, i.e., by an arctan or error function. For the
purpose of Fig. 7.18 we have used an error function step with the width of the n*
resonance. We note that in Fig. 7.15 the curve fit of the n* resonance actually
involved a Voigt profile and the ME step was a lineshape generated by
integration over this profile. For the chemisorbed spectrum in Fig. 7.15 the ME
step is slightly lower than the FL step. The shown fit used the ME step position
but a similar fit could also be obtained by use of the FL step and an increased n*
resonance intensity.
Finally, Fig. 7.19 shows curve fits of K-shell spectra of N2 in the gas phase
and for the weakly bonded y state adsorbed on Fe(111) [7.31, 32]. In this case
several steps are invoked. The fit of the gas phase spectrum is identical to that
shown in Fig. 7.11 b and the fits of the Rydberg and multielectron peaks have
already been discussed in conjunction with that figure and Fig. 7.8. For N2 on

Fig. 7.19. Curve fits of the N2 K·shell excita-

tion spectrum for (a) gas phase N2 recorded by
ISEELS [7.30], (b) NEXAFS spectrum of the
y state of N2 on Fe(lll) recorded at 10° graz-
ing X-ray incidence, and (e) as in (b) for normal
X-ray incidence [7.31, 32]. The N2 gas phase
spectrum is that of Fig. 7.1 lb. The NEXAFS
spectra of N2 on Fe(I11) also used Gaussian
and asymmetric Gaussian (0'* resonance)
peaks and error function steps as in (a), broad-
ened to account for lifetime effects. In addi-
tion, a ME step was included at the n* reson-
ance position (401 eV). We note that in a dif-
ferent model this latter step may be interpret-
395 405 415 425 435 445 455 ed as arising from a FL step at the lowest XPS
Excitation Energy (eV) binding energy of 401.2eV [7.53]
238 7. Analysis of K-Shell Excitation by Curve Fitting

Fe(111) the lowest energy step is a ME step at the position of the n* resonance,
as discussed for O 2 on Pt(111) above. For simplicity, the other steps were placed
at the same positions as in the gas phase spectrum in Fig. 7.19a. The Rydberg
and ME peaks have been broadened to account for the expected lifetime
shortening on the surface. The curve fits closely follow the experimental data,
and especially the normal incidence spectrum is fit considerably better than in
the original work by Wenzel et al. [7.31,32] who, however, used only one step
function.
The curve fitting of resonances and steps in molecular K -shell spectra is still
a matter of active exploration. The above discussion and the presented examples
should only be regarded as initial guidelines. Many open questions remain. With
an improved understanding generated by more detailed experimental studies
and by theoretical calculations which include substrate atoms in a realistic way
much may be learned about the excitation mechanisms themselves as well as
about the systems under study. The detailed understanding of energy positions
and intensities of peaks and steps should provide insight into the detailed
electronic interactions, e.g., adsorbate-metal wavefunction overlap, between
molecules and surfaces, and for multifunctional molecules about the differential
bonding between various subgroups of a given molecule and the surface. If
nothing else, realistic curve fits will lead to a more precise determination of
molecular bond lengths and orientations on surfaces.
8. (1* Resonance Position and Bond Length

In this chapter we review the evidence for a correlation between the 0"*
resonance position and the molecular bond length. In particular, we investigate
the question of whether and how the correlation found for simple free molecules
can be extended to large molecules and to physisorbed and chemisorbed
molecules.

8.1 Theoretical Predictions and the Search for a Correlation

The question of a correlation between the 0"* resonance pOSItIon and the
molecular bond length has been the subject of extensive discussions since the
early 1980s. The fundamental issues concerned the existence of a correlation
and/or the mathematical form of a correlation. Other questions dealt with the
extension of a correlation for simple molecules to conjugated molecules, or the
transferability of a correlation from free molecules to chemisorbed molecules. It
is clear that the existence of a reliable correlation between bond length and the
measured 0"* resonance energy would be of great practical importance, espe-
cially for chemisorbed molecules, where structural data are scarce. This chapter
gives a critical assessment of the existence of such a correlation, and of its
reliability and its limitations. Before we discuss various theoretical and experi-
mental aspects of the correlation we give a brief review of its history.
The first clear prediction of a quantitative correlation between the 0"*
resonance position and the molecular bond length emerged in 1979 from the Xa
MS calculation of Dehmer et al. [8.1] on nuclear motion effects in N z . The most
relevant results of this calculation have already been presented in Fig. 4.7.
Although the calculation was carried out not for K-shell excitation but for that
of the 30"g valence orbital (Fig. 2.5), it clearly shows the strong dependence of the
0"* resonance position on internuclear distance. In fact, it predicts a resonance
shift of about 15 eV to lower energy for an increase of 0.26 Ain the N-N bond
length. The existence of a correlation was also revealed by Stieltjes-Tchebycheff
MO calculations by Langhoff and co-workers on various molecules [8.2]. These
authors state in a 1980 review [8.3]: "the positions ofthe 0"* orbitals in first-row
diatomics are found to be dependent upon bond length, with short bond lengths
giving high-lying 0"* orbitals, and long bond lengths giving low-lying 0"* orbitals,
240 8. (1* Resonance Position and Bond Length

in accord with the behavior of energy levels in one-dimensional wells." We shall

come back to the correlation with energy levels in a well later.

°
From photoemission data on shape resonance positions in dil:}tomics such as
CO, N 2 , NO, and 2 , Gustafsson and Levinson [8.4] argued in 1981 that the 0'*
resonance position, measured from the vacuum level, should vary with intra-
molecular bond length R as 1/R2. In the same year, Hitchcock and Brion [8.5]
showed that all previously suggested correlations between bond lengths and 0'*
resonance positions failed when the experimental data set was extended to
"pseudodiatomics" such as C 2 H 2 , HCN and H 2 CO, and to the newly measured
diatomic F 2 molecule. Instead, these authors proposed that the resonance
position depended largely on the sum of atomic numbers of the bonded atoms, Z.
In 1983 Natoli [8.6] published a discussion on the origin of 0'* resonances in the
framework of potential scattering theory and pointed out that under certain
simplifying assumptions the complicated multiple scattering equations for the
resonance energy reduce to the simple form

(8.1)

Here AO' is the 0'* resonance position relative to the vacuum level; in accordance
with the definition used in Chap. 4, the constant Co depends on the atomic
scattering phaseshifts; R is the bond length and Vo (generally a negative number)
is the muffin-tin or "inner" potential as defined in Fig. A.1. This model was used
by Bianconi et al. [8.7] to explain the trends in 0'* resonance positions observed
for N 2 , CO, NO, C 2 H 2 , and C 2 H 4 in the gas phase and by Stohr et al. [8.8] for
chemisorbed CO, formate (HCOO-), and methoxy (CH 3 0) on Cu(100), and for
O 2 on Pt(111).
In 1984 Sette et al. [8.9, 10] set out to derive an empirical correlation
between the 0'* position and intra-molecular parameters, using a large data set
of experimental K -shell excitation spectra. By classifying molecules into groups,
characterized by Z, the sum of atomic numbers of adjacent, bonded atoms, as
previously proposed by Hitchcock and Brion [8.5], a remarkably simple linear
relationship of the form

AO' = -aR +b (8.2)

was obtained between the bond length R and the 0'* resonance position relative
to 1s ionization potential, AO'. Equation (8.2) with a > 0 was shown to hold
within each Z-group. Sette et al. also pointed out that the observed linear
correlation was compatible with the 1/ R 2 dependence predicted by theory [8.6]
if the inner potential Vo was a function of both the bond length R and the sum of
atomic numbers of the bonded pair, Z. In more general terms, it was also argued
by Sette and Stohr [8.11] that over the limited range of molecular bond lengths
(1.1-1.5 A) any functionf(R) ex 1/ R2 can be approximated by a linear function
of the form given by (8.2) to within a few percent. Within the same year this
 8.1 Theoretical Predictions and the Search for a Correlation 241

simple model was also shown to be of great predictive power for the bond
lengths in both free [8.12J and chemisorbed hydrocarbons [8.13J, and the
linearity of the correlation of resonance position with bond length led to the
phrase "bond lengths with a ruler" [8.13J. The empirical correlation of Sette
et al. [8.9-11J was criticized in 1987 by Piancastelli et al [8.14, 15J who
questioned some of the assignments of the 0'* resonances in the experimental
data and pointed out the failure of the correlation to properly account for the
resonance positions in triatomic conjugated molecules like CO 2 ,
In response to the ongoing debate [8.16J, Sheehy et al. [8.17J addressed the
problem in 1989 with ab initio MO calculations. By use of a simple one-
dimensional square well, modelled after the shape of the potential in the valence
region as illustrated for a diatomic in Fig. 8.1, these authors found that the 0'*
position relative to the vacuum level was closely described by the correlation

(8.3)

where h is Planck's constant, m the electron mass, n the characteristic quantum

number of the energy level in or above the well, L the width of the well
(determined by the molecular geometry), and U o (a negative number) the well
depth, which can be obtained from MO calculations. Note that (8.3) with L = R
and Uo = Vo has the same functional form as (8.1), showing the close corres-
pondence between the MO and scattering pictures.
In the following sections we deal with the theoretical and experimental
aspects of the correlation in more detail.

I·I L ·1I
I
-=::--\----"1 - - - -
I Vacuum Level
Uo

Atom-€) . _ Atom
A I--R---I
I I
B

Fig. 8.1. Schematic of the potential for a diatomic molecule and its approximation by a one-
dimensional square well potential, with the directional coordinate chosen along the internuclear
axis. The square well is a rough approximation of the potential felt by the outer valence electrons. It
is characterized by a length L, related to the overall length ofthe molecule, and depth Uo, related to
the value of the potential between the two atoms. Note the close correspondence of Uo to the "inner
potential" Va used in a muffin-tin approximation of the potential, as illustrated in Figs. 2.7 and A.l
242 8. u* Resonance Position and Bond Length

8.2 Predictions by Scattering Theory

Possibly the easiest way of deriving the correct functional form of the correlation
between bond length and cr* resonance position, in a scattering picture, is by use
of the EXAFS equation (2.63), which for two atoms separated by a distance R
can be written in simplified form as

X(k) = A(k) sin [2kR + 4J(k)] , (8.4)

where A(k) is the amplitude function, and 4J(k) the total scattering phase shift
with contributions from the two bonded atoms. Let us assume that the cr*
resonance corresponds to the first EXAFS maximum, which according to (8.4)
occurs at 2k"R + 4J(k) = n12, where k" is the photoelectron wavevector at
resonance. If we further assume that 4J(k) ~ const over the (small) energy range
of the cr* resonance, we obtain

(8.5)

where the constant depends on the atomic scattering phase shifts. As discussed
in Appendix A, the wavevector scale has its "zero" at the muffin-tin potential
Vo < 0 below the vacuum level; see Fig. A.I. Denoting the cr* resonance position
relative to the vacuum level by Il", as in Chap. 4, we can write [compare (A.17)]

k = Fm(1l - V. )1/2 (8.6)

" h " 0

such that k" = 0 for Il" = Vo. The cr· resonance can therefore lie above (Il" > 0)
as well as below (Il" < 0) the vacuum level, the only restriction being that it has
to lie above the muffin-tin energy Vo. Substitution of(8.6) into (8.5) leads to (8.1),
given above, and the model therefore predicts that the cr* resonance position
varies as 1I R 2.
The same result is obtained from Xcx-MS theory as discussed by Natoli
[8.6, 7]. In this case one starts with the determinant of the multiple scattering
matrix in K-matrix asymptotic normalization, which must vanish at resonance.
This leads to an implicit relation involving as parameters the wavevector k" at
resonance, the distance vectors Rij of the va~ious atomic scattering centers in the
molecule, and the associated phase shifts c5:(k,,). Under the assumptions that (i)
at k = k" the zero of the determinant is sensitive predominantly to one particu-
lar distance R in the molecule, (ii) the atomic phaseshifts c5{(k,,) are transferable
between different systems under study, and (iii) the dependence of the phase
shifts on energy is smooth near k = k", the vanishing of the determinant is found
to reduce to the simple relation expressed by (8.5). Then the same arguments
given above lead to the result given by (8.1).
Justification for treating cr* resonances like the first EXAFS maximum has
been provided by Xcx-MS calculations for O 2 and N2 by Stohr and Bauchspiep
[8.18]. A theoretical study of these two molecules is particularly interesting
 8.2 Predictions by Scattering Theory 243

(a) Vacuum
(b)
o
Level
:;-
- 20 ~ -20
Latter Latte r
> -40
~
Tail Tail '.::.. - 40
>
E -60 - 60
>
- 80 Core
Hole
- 100 -2 -1 0 1 2
Distance from Molecular Center (A) z

Fig. 8.2a~. Molecular potential for the spin-up electrons in the O 2 molecule calculated with the XIX-
MS method [8.18]. (a) Cut of the potential in the plane containing the nuclei. For distances larger
than 1.75 Afrom the molecular center the XIX potential has been substituted by a Coulomb potential,
marked "Latter tail". (b-d) Three-dimensional plots of the potential, showing its shape to different
depths below the vacuum level, the latter corresponding to the energy zero

because the (J* resonance falls above the IP for N2 while it is bound for O 2, as
discussed in Sect. 4.3. Because of the sensitivity of the calculated NEXAFS
structure to the details of the molecular potential, the transition state potentials
for both molecules were first constructed to yield the correct Is IPs. The N2
potential and the continuum cross sections have already been shown in Fig. 4.10
(see also Fig. 4.4). For O 2 the (spin-up) potential is shown in Fig. 8.2 and the
calculated NEXAFS spectrum is that of Fig. 4.l4a. Using these molecular
potentials Stohr and BauchspiejJ calculated the extended fine structure up to
about 500eV above the IPs. This was simply done by including higher angular
momenta in the partial wave expansions, where the choice of Imax has been
discussed in conjunction with (A.32). The results of the calculations are shown in
Fig. 8.3, where the (J* resonance and the EXAFS signal are plotted as a function
of the wave-vector k above the muffin-tin zero. The O 2 calculation is also
compared to the experimental results of Yang et al. [8.19,20].1 Unfortunately,
at present no experimental EXAFS results have been published for N 2.

1 The O 2 spectrum shown here was provided by BX Yang (private communication) and differs
slightly from those published previously.
244 8. (J* Resonance Position and Bond Length

Oxygen Molecule Fig.8.3. K-sheIl X-ray absorption

fine structure of (8) O 2 and (b) N2
,
N 0* - Experiment
molecules as a function of wave vec-
1
~
N
xa ---- Xa - MS Theory
tor k, calculated by means of the
-'"
:;< 1 XIX-MS method. For O 2 the calcu-
N lation is compared to the experi-
(ij mental data (solid line) of [8.19, 20],
c
~ O~~~~~~U---~----~--~~~~
and the (J* resonance intensity near
k = 2.8 A- I is reduced by factors of
(/)
u. 3 and 8 for the experimental and
>=i theoretical curves, respectively. In
UJ -1
both cases we have plotted the fine
structure amplitude X(k)P. For O 2
we have used the value Eo
2 4 6 8 10 = 514.4eV as the energy zero for
Wave Vector k ( A-') our wave vector scale calculation.
This value corresponds to the cal-
Nitrogen Molecule
_ 20 culated muffin tin zero, 29.2eV be-
N
, 0* low the average Is IP (543.65eV).
00(
Xa - MS Theory For N 2 , the muffin tin zero faIls
-16
N 25.8eV below the vacuum level,
-'"
;g 12
and the energy zero was chosen at
~ IP 384.1 eV, 25.8 eV below the Is IP
(ij

1
c ([Link])
8
en
C)

(/)
u. 4
«
x
UJ
0

-42 4 6 8 10 12
Wave Vector k (A-' )

The interesting point about Fig. 8.3 is the position of the 0"* resonance
relative to the positions of the EXAFS maxima. For both molecules one can
roughly predict the 0"* position from extrapolation of the EXAFS structure. As
indicated by a bar diagram, for O 2 the two EXAFS maxima near 6 and 9 A- 1
are separated by Ak ~ 3.1 A-i. EXAFS theory would therefore predict the next
lower maximum just below 3 A- 1, which is indeed the observed position of the
0"* resonance. For N2 the position of the 0"* resonance and the EXAFS maxima
are moved to higher k-values, as expected from the shorter bond length. Again,
the spacings between the 0"* position and the two EXAFS maxima are roughly
constant. The results shown in Fig. 8.3 therefore support the simple EXAFS-like
scattering picture used above to explain the distance dependence of the 0"*
resonance position.
It is interesting to explore the origin of this behavior from inspection of the
scattering potential for O 2 shown in Fig. 8.2. This potential has two clearly
visible main components. The muffin tin part is determined by the detailed
valence electron charge distribution, with a radius about equal to the bond
 8.3 Predictions by Molecular Orbital Theory 245

length and a depth given by the inner potential, and corresponds to the well
shown in Fig. 8.1. This well is superimposed on the atomic core components.
The importance of the muffin tin well is that its depth is responsible for fixing the
energy zero of the photoelectron, and therefore the zero of the EXAFS scale. In
contrast to conventional EXAFS theory, where effects due to valence electron
charge overlap are typically ignored [8.21, 22J, for low-Z molecules the effect of
this well is felt even in the EXAFS region, where it manifests itself in a phase shift
offset [8.18, 19,23]. We note that the more recent EXAFS theory of Rehr et al.
[8.24, 25J properly accounts for valence electron effects, and results obtained
with this single scattering theory do agree with the X<x-MS results for O 2 [8.18J
shown in Fig. 8.3 in the region k > 4 A- 1. The reason for the importance of the
valence electron charge distribution for low-Z molecules lies in the large fraction
of valence electrons relative to the total number of electrons in such systems, and
the short covalent bonds in such molecules. This causes the inner potential to be
large, e.g., about - 29 eV for O 2 • Hence, for low-Z molecules, both the valence
and core electron charge distributions are important in determining the molecu-
lar scattering potential and this is the reason for the close link between the (1*
resonance position and the positions of the EXAFS wiggles.

8.3 Predictions by Molecular Orbital Theory

The basis of a correlation of (1* resonance energy and bond length in a MO

picture comes from a consideration of the eigenvalues of an electron in a
potential well, as discussed by Sheehy et al. [8.17]. In this potential-well
formulation the eigenvalues represent the energies of filled and more import-
antly unfilled MOs, the latter corresponding to (1* resonances, and the length of
the potential well is characteristic of the molecular dimension, which is related
to the bond length as shown in Fig. 8.1.
In deriving the desired correlation let us first consider the energy levels and
wavefunctions of a one-dimensional square well potential of infinite depth,
defined as

U(x) = 0, - Lj2 < x < Lj2 ,

= + 00, Lj2::;; Ixl. (8.7)

This potential has impenetrable walls at the points x = ± Lj2. The eigenvalue
solutions to the wave equation are given by [8.26J

(8.8)

and there is thus an infinite sequence of discrete energy levels corresponding to

positive integers of the quantum number n. Expressing En in units of eV and Lin
246 8. a* Resonance Position and Bond Length

A, we obtain the "well constant" as h2 j (8m) = 37.6 eV A2 . Each energy level has
an associated eigenfunction given by

n odd, (8.9a)

and

Un(X) = B sin ( n~x ) n even, (8.9b)

with normalization constants A and B. The potential well and the eigenvalues
and eigenfunctions as a function of n are plotted in Fig. 8.4a.

(8) (b) (c)

co

3a~ ,dl 4lUt _

___.-: "::"-'-;-::;;'~- ' n= 4- - - -
- n

~-QfiU9.-4'JllA,y
rmml"
-"-rr-

~4 ~a

--- --- ... -

,' .-
. - - - . . ~ n == 1- . .

- L-

Fig.8.4. (a) Schematic of the energy levels and wavefunctions in a one-dimensional square well
potential. The well has a width L and infinitely high walls. The energy levels are labelled by the
quantum number n. (b) Occupied (2a., 2au , and 3a.) and virtual (3a!) MOs ofN 2 , obtained from a
minimum basis set calculation, plotted in a plane parallel to but shifted off the internuclear axis by
O.42A [8.17]. The virtual orbital is constructed in the (3a g )-! hole-state potential. The orbitals are
enclosed in a finite well of length L determined by the molecular geometry, and depth Uo , obtained
from a MO calculation [8.17]. (e) MOs of (b) plotted in a plane with dimensions 6.4A by 4.2A
which includes the two nuclei. The Coulomb cusps fall at the positions of the nuclei. In all cases the
energy separations shown are not to scale
 8.3 Predictions by Molecular Orbital Theory 247

When the eigenfunctions shown in Fig. 8.4a are compared to u-type molecu-
lar orbitals of N 2, calculated by a minimal basis set MO calculation [8.17],
shown in Fig. 8.4b, the resemblance is striking, and it is easy to establish an
unambiguous assignment of n values to the MOs. Note that in using a one-
dimensional potential well model we only consider motions of the trapped
electron in one direction, which we have chosen (compare Fig. 8.1) to lie along
the internuclear axis, hence n-type orbitals are not accounted for. Also, we have
implicitly assumed that the well models the potential seen by the valence
electrons only, and hence in Fig. 8.4b the N2 Is (luu and lUg) orbital is not
considered. In pseudodiatomic molecules containing bonds to hydrogens, the
quantum number n refers to the nodal pattern of the orbitals in the C-O or C-C
bonds only, and there might be more than one MO associated with a single n
value [8.17].
The close correspondence between the particle-in-a-box wavefunctions
shown in Fig. 8.4a and the minimal basis set MOs shown in Fig. 8.4b, on one
hand, and the functional form of the eigenvalues given by (8.8), on the other
hand, led to the idea of introducing a finite potential well of depth U 0 and length
L, as shown in Figs. 8.1 and 8.4b. The top of the well corresponds to the vacuum
level, such that we can denote as An the energy separation of the nth orbital from
the top of the well. In particular, for the N 2 molecule as shown in Fig. 8.4b, the
0'* resonance position relative to the vacuum level A" is given by .1 4 > O. In
analogy to (8.8), we can then, in this finite-well picture, try a correlation of the
form

(8.10)

where the parameters C, L, and U 0 are determined as discussed below. First, we

need to explain why a one-dimensional potential well might be a reasonable
description for a molecular potential. Plots of the valence MOs ofN2 in a plane
containing the nuclei, shown in Fig. 8.4c, indicate that the MOs appear to decay
in the radial direction (perpendicular to the internuclear axis) in a nodeless,
largely uniform fashion, independent of the position along the internuclear axis.
Note that, along the internuclear axis, the orbitals plotted in Fig. 8.4c differ from
those in Fig. 8.4b mainly in that they contain cusps at the positions of the nuclei.
The N2 potential can therefore be modelled by a cylindrical potential well with
the cylinder axis parallel to the internuclear axis. The cylinder has a radius Po
and length L, and the potential has the value U 0 inside and zero outside the
cylinder. Again, L is related to the "length" of the molecule, as discussed below.
Since the quantum number associated with the radial coordinate Po does not
change for the 0' orbitals of interest here, the problem focuses on the cylinder
length L and the potential depth Uo , reducing the model potential to that of a
one-dimensional square well as shown in Figs. 8.1 and 8.4b.
In this model, the well length L for a molecule is not identical to a particular
internuclear distance (i.e., bond length) or the sum of internuclear distances, but
248 8. u* Resonance Position and Bond Length

instead is obtained by adding the lengths of the terminal bonds on the periphery
of the molecule to the internuclear distance(s) [8.17]. The difference between
bond length and length of the potential well is clearly revealed by Fig. 8.1. For
N2 with a bond length of R = 1.095 A, for example, a terminal bond length of
the same value is added on each side of the molecule, and hence
L = 3R = 3.285 A. For CO 2 with Rc=o = 1.16 A we have a sum of bond lengths
of twice that value, and need to add terminal bond lengths of 1.16 A on each side
of the molecule, yielding L = 4R = 4.64 A. In the case of nonlinear pseudodi-
atomics with hydrogen bonds, only the effective C-C or C-O well lengths are
used, e.g., for H 2C=CH 2 L = 3Rc =c = 4.011 A. For linear diatomics with hy-
drogen bonds, a terminal bond length is added on each side of the molecule
which is equal to the bond length of the terminal atom, e.g., for H-C:=N,
the bond lengths are RC-H = 1.065 A and RC;N = 1.158 A, yielding L = 2Rc-H
+ 2Rc;N = 4.446 A.
The well depth U0 and constant C in (8.10) are determined by a least-squares
fit to the (n 2 , An) data points for each molecule, calculated by a minimal-basis-set
MO calculation, with the n-values assigned by comparison to the eigenvalues
and eigenfunctions of the infinitely deep well (8.8, 8.9). For this comparison to be
meaningful it is important that, as proven by Sheehy et al. [8.17], the energy
positions of the minimal basis set MOs agree well with the positions calculated
with the extended basis set ST-MO technique (Sect. 2.8). The lowest unfilled
MO, or MOs in the case of polyatomic molecules, will then be associated with
the 0"* resonance(s). An example is the 30": MO in Fig. 8.4b, corresponding to
n = 4. Another example is CO 2, where the 50": and 40": orbitals shown in Fig.
3.2 are associated with n = 5 and n = 6, respectively. Hence this scheme natu-
rally includes conjugated molecules, with more than one 0"* resonance.

4
K Shell Excitation /
/
/

Fig.8.5. Correlation between K-shell u*

resonance position ~. and the square of
3 the inverted well length 1/ L 2 according to
> (8.10). The values for ~. were obtained
~
N
<: from experiment, a minimum basis set cal-
:::::. culation and ab initio Stieltjes-Tchebycheff
I
MO theory [8.17] with the label n of the
:;!'" 2 first unfilled MO or MOs identified by
comparison with the nodal pattern of the
wavefunctions according to (8.9a) and
(8.9b). The well depth Uo and well constant
C were determined by least-squares fit to
o Min. Basis Set Calc. the (n 2 , ~.) data points for each molecule
/),. Experiment
o ST·MO Calc. [8.17]. The dashed line corresponds to the
well constant C = h2/(8m) = 37.6eV A2 of
0.02 0.04 0.06 0.08 0.10 a one-dimensional infinitely deep square
l/L2 (.$,,-2) well potential, according to (8.8)
 8.4 Empirical Correlation for Simple Free Molecules 249

The correlation obtained by Sheehy et al. [8.17] between the positions ofthe
lowest unfilled MOs, calculated by minimal basis set and ST-MO calculations
for K -shell excitation, and 1/ L 2 is shown in Fig. 8.5. Experimental data points
are also included. The figure was constructed by using theoretical or experi-
mental values for ~n (theory) or ~O" (experiment) and corresponding n-values
obtained by comparison with eigenvalues and eigenfunctions of the infinitely
deep well (8.8, 9). For each molecule the well depth U 0 and well constant C in
(8.10) were determined by least-squares fit as mentioned earlier. The dashed line
through the data points in Fig. 8.5 corresponds to the well constant
C = h2 /(8m) = 37.6 eV A 2 of the infinitely deep well according to (8.8). Figure
8.5 clearly establishes a correlation according to (8.10) and the well constant Cis
in surprisingly good agreement with that of a simple one-dimensional square
well with width L and infinitely high walls. In retrospect, this agreement gives
credence to the original idea of using a simple well model.

8.4 Empirical Correlation for Simple Free Molecules

The basis for an empirical correlation between a* resonance position and bond
length has already been discussed in Sect. 4.3. We shall here follow our earlier
selection, concentrating on simple non-conjugated molecules of various bond
types, characterized by the sum of atomic numbers of an atomic pair, Z. The
data for the relevant molecules are summarized in Table 4.2. A similar data base
was used by Sette et al. [8.9, 10] in their original work which proposed the
empirical correlation to be discussed below. Here we have eliminated conjuga-
ted molecules such as benzene and added data of some newly measured
molecules such as H2N-NH2 [8.27], F 3C-NO [8.28] and HO-OH [8.29]. It
should be noted that all new data fit remarkably well into the originally
proposed scheme [8.9, 10].
The correlation between bond length Rand a* resonance position relative to
the IP, ~O", is shown in Fig. 8.6. For each bond type, characterized by Z, the
resonance position decreases monotonically with increasing bond length, and
within error bars, the correlation is linear within each Z-group. The error bars
shown in Fig. 8.6 reflect the accuracy with which the a* position could be
determined from the experimental data and/or the spread in ~O" values if more
than one K -shell was studied in a given molecule (Table 4.2). The slope of the
straight lines drawn through the data points in Fig. 8.6 is similar for Z = 12 and
Z = 13, with values of about 5.5eV/0.1A and 4.5eV/0.1A, respectively. A
smaller value of about 3eV /0.1 A is observed for Z = 14 and 15 and 2eV /0.1 A
for Z = 16. At present, only a single data point each is known for F -0 bonds
with Z = 17 and F - F bonds with Z = 18. Especially for Z = 12 and 13, there is
great sensitivity of the resonance position to bond length, in principle, of the
order of 0.01 A, c~rresponding to a resonance shift of 0.5 eV.
250 8. u* Resonance Position and Bond Length

20

:;-
~ 15
~
E 10
e
:2 5
'iii
o
c.. 0
Q)
u
c:
~ -5
o
III
Q)

a: -10
'0

-15
1.10 1.20 1.30 1 .40 1.50 1.60
Bond Length. R (Al

Fig.8.6. Empirical correlation between the u* resonance position relative to the Is ionization
potential (IP) and the bond length R for simple, non-conjugated molecules. All data are from K-shell
spectra of free molecules, summarized in Table 4.2. Each data point is labelled by the molecule it
represents and the bond and bond type is explicitly indicated. The molecules are grouped according
to the sum of atomic numbers of the bonded pair, Z

8.4.1 The Energy Reference Question

In our previous discussion we have used the 0'* resonance position relative to the
IP. In doing so we could conveniently combine the data obtained at different K-
edges, as discussed in Sect. 4.3. In general, this scheme eliminates all chemical
shifts in the Is binding energy arising from different bonding environments of
the same atom. Let us briefly take a closer look at chemical shift effects. For
hydrocarbons, chemical shifts are relatively small, typically less than 1 eV, as
revealed by Table 4.2, and shown in Fig. 8.7. The reason is the small electro-
negativity difference of carbon and hydrogen. Changes in the number of C-H
and C-C bonds about a given C atom, i.e., hybridization, does not have a strong
effect on the charge at that atom and thus on the CIs IP. For example, the Is IP
differs only by 0.4 eV between single bonded ethane (290.7 eV) and triple bonded
acetylene (291.1 eV). Therefore we can also establish an approximately linear
relationship between the C-C bond length and the absolute 0'* resonance
energy, Ea , as demonstrated in Fig. 8.7. This fact was first utilized by Arvanitis
et al. [8.30] for the study of chemisorbed hydrocarbons.
The situation is more complicated for more electronegative atoms, such as
oxygen, and Table 4.2 and Fig. 8.8a reveal large chemical shifts up to about 4eV
for C-O bonds. The most dramatic cases are encountered for C-F bonds (Figs.
4.15 and 4.16), where chemical shifts in excess of 5 eV are encountered. In such
cases the relationship between bond length R, and absolute 0'* position, Ea , may
no longer be linear as shown for C-O bonds in Fig. 8.8(a). On the other side, in
 8.4 Empirical Correlation for Simple Free Molecules 251

20
310 :;-
:;- ~
~

,...'"
15 w
<I '" 305
e; e>
B 10 '"
c:
300 ~
~
c:
5
.."
c:
c:
~ 295 ~
'iii
0 II:
Q.
"",
"", 0
290

1.2 1.3 1.4

Bond Length, R (A)

Fig.8.7. Correlation between (1* resonance position and bond length R for C-C bonds. The data
points are those of Fig. 8.6, i.e., those of acetylene, ethylene, and ethane. The two solid curves
correspond to a linear (oc. -R) and an inverse quadratic (oc.l/R2) relationship, respectively,
between the (1* position and the bond length. Because of the insensitivity of the C Is ionization
potential (IP) to bond hybridization, the data points R can be plotted to a good approximation as a
function of either d., the (1* resonance position relative to the IP (left ordinate), or E., the absolute
(1* resonance position (right ordinate)

:;;-
(al "
550 -to
Coo Bonds w
548 >.
~
CD
546 ~

..g
CD
:;;- OK-edge 544

.
~ c:
to 542 ~
~ 304 '6 ,,
..
II:
,,
>.
e> 540.",
c: 302
w
." 'eo ,
,,
538
c:
~

.
c:
300
,,
>.
0"

..
c:
.,
0 298
IP ,, C K-edge
II: 296 ........ .... ,,
'", .... ,,
of!
c: 294

.
0

292
~
-- ---~
,
Fig.8.8. (a) Absolute (1* resonance energy,
U
:;;- E., ofC-O bonds as a function of bond length,
(b)
~ 8 'Q for oxygen and carbon K-shell excitation. The
to
three data points and the respective ionization
<I
e; 6
~'A ........ C K-edge potentials (IPs) correspond to carbon monox-
g 4 ' ,, / ide, C=O, formaldehyde, H 2 C=O, and meth-
.... ,
ec: 2 OK-edge
,, anol, H 3C-OH (see Table 4.2). (b) (1* reson-
.... , ance position relative to the Is IP as a function
~ 0
'iii
0
of R, for oxygen (solid line) and carbon (dashed
.
Q.
-2 line) K-shell excitation. The line for Z = 14 in
'
1.1 1.2 1.3 1.4 Fig. 8.6 represents the average straight line
Bond Length, R (.8.) shown here
252 8. u· Resonance Position and Bond Length

this case the position of the u~ resonance follows the change in the IP, leading to
an essentially linear dependence (within 0.5 eV) of L\.. with R, as shown in Fig.
8.8b.
Chemical shifts for 0-0 bonds are slightly smaller, about 2 eV between
0=0 and HO-OH, but they are still significant. Data for these two molecules
[8.29] are shown in Fig. 8.9, and an additional data point has been included,
namely that for bis-triftuoromethyl peroxide (CF 30-0CF3)' which has a bond
length of 1.419 ± 0.020 A [8.31] and a u* resonance at 533.6eV [8.32]. Unfortu-
nately, no data point for an intermediate 0-0 bond length in the 1.30-1.35 A
range is available, which would show whether the dependence ofthe absolute u*
position, E.. , on bond length, R, is better described by a linear (oc - R)
or inversely quadratic (oc 1/ R2) relationship. As shown at the bottom of Fig.
8.9, a linear correlation is found to be a good approximation for the dependence
of the relative u* position, L\.. , with bond length. In this case the data set can be
augmented with results for N-F bonds, as shown.

0-0 Bonds ::;-

~
544 e:
-..................

0=0
------IP
542 ~
"0

b
540 W
>.
538
e>
Q)
co
E.. W
::;- 536 ~
~ 0 co
b 534 §'"
<I -2 VI
Q) Fig. 8.9. Ionization potential (IP), absolute u·
532 cr: resonance energy, E a , and u· energy relative to
g -4 'b
the IP, /la' for three molecules (filled circles)
! -6 with 0-0 bonds as a function of bond length R
co [8.29]. The data points for Ea have been connec-
o
:;::; -8
'iii
ted with a straight line and a 1/ R2 curve. In the
o
Q..
bottom curve we have also included data points
'b 1.2 1.3 1.4 1.5 for two molecules with N-F bonds. This curve
Bond Length, R (Al corresponds to the line for Z = 16 in Fig. 8.6

8.4.2 Bonds Involving High-Z Atoms

An interesting question concerns the bond-length sensitivity of u* resonances
for bonds between first row low-Z atoms such as C, N, 0, and F and heavier
atoms with Z> 10. As an example we show in Fig. 8.10 the carbon K-shell
spectra of the methyl halides (H3C-X), with X = F, CI, Br, and I [8.33]. The
molecules cover a large range of bond lengths Rand Z values, i.e., R = 1.382A
and Z = 15 for H3C-F, R = 1.785 A and Z = 23 for H3C-CI, R = 1.933 A and
Z = 41 for H3C-Br, and R = 2.132 A and Z = 59 for H3C-I. The assignment of
the resonances indicated in Fig. 8.10 follows from Fig. 4.17. Here our interest
 8.4 Empirical Correlation for Simple Free Molecules 253

C K -Shell Fig. 8.10. ISEELS carbon K -shell excitation spectra

of methyl halides [8.33]. The lowest-energy peak
corresponds to the a* resonance associated with the
C- X bond, where X = F, CI, Br, or I. The higher
energy resonances are associated with
Rydberg j C-H* orbitals, and exhibit vibrational fine
structure. All resonances follow the trend of the IP,
but the ac - x resonance increases its separation from
the IP from~. = - 4.4eV for CH3F to -5.7eV for
CH3I

284 286 288 290 292 294

Electron Energy Loss (eV)

focuses on the movement of the lowest energy (1t-x resonance relative to the IP.
Although there is a systematic trend with ~a, i.e. - 4.4eV (H3C- F), - 5.0eV
(H3C- C1), - 5.3eV (H3C-Br), and - 5.7eV (H3C-1), the changes are very
small in consideration of the large change of Rand Z. The insensitivity of ~a to
Rand Z for the methyl halides and for a large number of sulfur-containing
molecules [8.34] is convincingly illustrated in Fig. 8.11. Here we have also
incorporated for comparison the results for simple low-Z molecules shown
earlier in Figs. 4.18 and 8.6. Clearly, for bonds involving second row atoms and
heavier atoms with Z ;;::: 16, the (1* resonance always falls at an energy around
5 eV below the IP, and its sensitivity to bond length is greatly reduced, if not lost.
It appears that one can only hope to obtain structural information from subtle
shifts within a group of closely related molecules or compounds.
At first sight our conclusions seem to be inconsistent with the bond length
correlation proposed by Lytle et al. [8.35] for ceramic superconductors and
Kasrai et al. [8.36] for minerals, where the bonds involved high-Z atoms. It
should be noted, however, that in these latter cases the correlation involved
higher energy resonances in the continuum region while in Fig. 8.11 we have
only discussed the lowest energy (1* resonance position, falling below the IP. If
one envisions that the lowest energy (1* resonance corresponds to the first
254 8. CT- Resonance Position and Bond Length

20 R-Dependence
15 ~-C
':~~~~~ ...............N-N
C-F~
.
o
~
<I'" -
5
-.......N-O-.......~
N-F
0 - 0-"""""'::: F-S
COS C-CI
....JS==~:;;:;:;;;:::t::::J
C-Br
.
C- I

a: -10 O- F ... O- S
B -15 F- F •

1.1 1.2 1 .3 1.4 1.5 1 .6 1.7 1 .8 1.9 2.0 2 .1

c
g Bond Length. A (.8..)
'Vi
o
Q.
C1>
u
c
Z-Dependence
'"
c
.,'"
o
a:
'b

-10

- 15
12 14 16 30 40 50 60
Sum of Atomic Numbers. Z

Fig.8.11. Illustration of the insensitivity of the CT* resonance position to bond length, R, and sum of
atomic numbers of bonded pair, Z, for bonds between C, N, 0, or F atoms and high-Z atoms. The
data for Z < 20 are taken from Fig. 8.6 and Fig. 4.18, those for Z > 20 from Fig. 8.10 and a review
by Hitchcock [8.27]. Note that for Z < 20 the CT- resonance position relative to the IP, ~., is a
sensitive function of both Rand Z, while for larger Z-values, a nearly constant value of~. "" - 5eV
is observed

EXAFS maximum, n = 1, and the higher energy resonances reflect the higher
order (n = 2, 3 ... ) EXAFS maxima (Sect. 8.2), one would expect a correlation
of the type

2n - 1
2kn R + <I>(k) = - 2- 1 t . (8.11 )

Assuming that over the limited near-edge region the phase shift can be approx-
imated by a linear function <1>( k) = a - bk, it is easy to show by use of (8.11) that
the change of the energy positions of the EXAFS maxima En with bond length R
has a functional dependence given by

dEn 1 2
dR = (R _ b/2)3 [An + Bn + C] , (8.12)
 8.5 Correlation for Large Molecules 255

where A, Band C are constants of comparable magnitude. Therefore, the shift of

En due to a bond length change drastically increases with n, making the higher-
order maxima more sensitive to changes in R. This result, which is the basis of
the high sensitivity of EXAFS to bond lengths, can explain the results of Lytle
et al. and Kasrai et al. [S.35, 36].

8.5 Correlation for Large Molecules

So far we have restricted our discussion to diatomic or pseudo-diatomic

molecules. As discussed in Chaps. 4 and 6, these systems are characterized by
only one 0"* resonance (ignoring hydrogens). For larger molecules more than
one resonance is observed, due to either the presence of more than one bond
type (building block picture) or the effects of conjugation in the 0" system. As in
Chap. 6 we shall treat these cases separately. Furthermore, we shall distinguish
between chain-like and ring-like molecules in the discussion of molecules
containing different types of bonds. This will allow us to assess the possible
effects of ring strain.

8.5.1 Chain-Like Hydrocarbons with Alternating Bonds

Within the building block picture one would expect the different 0"* resonance
positions to correlate with the lengths of corresponding bonds. Because of their
importance and their extensive treatment in textbooks let us begin our dis-
cussion with "linear" hydrocarbons with alternating bonds, the simplest cases
being propene (H 3 C-CH=CH 2 ), also called propylene, and methylacetylene
(H 3 C-C==CH), also called propyne. Their theoretical spectra have already
been discussed in Sect. 6.3.3 in conjunction with the building block picture. In
the previous qualitative discussion we neglected, however, the quantitative
aspects of the bond lengths. In particular, we assumed that the bond lengths in
propene were identical to those in the building blocks ethane and ethylene, and
those in methylacetylene were simply those of ethane and acetylene. In reality,
this is not true as revealed by Table S.1. In both molecules the C-C single bond
length is reduced below the nominal single bond len~th of 1.533 A found in
ethane. The "single" bond length in propene is 1.506 A, while that in methyl-
acetylene is 1.45S A[S.37], a sizable 0.075 A reduction! In contrast, the double
and triple bond lengths are the same as those in the building blocks to within
0.01 A.
The origin of the shortening of the C-C "single" bond length in alternating
hydrocarbons has been the subject of some controversy [S.4S]. The first
explanation dates back to 1939, when Pauling et al. [S.49] proposed it to arise
from "resonance" between the two adjacent C-C and C = C or C == C bonds,
thereby giving the single bond some unsaturated character. These qualitative
ideas were founded on a molecular orbital treatment by Mulliken and coworkers
256 8. u* Resonance Position and Bond Length

Table 8.1. u* resonance positions and Is ionization potentials in selected large molecules

z· Molecule b Is Ipc Eal Ea, Aa, Aa, Ref. R~ Rd2

[eV] [eV] [eV] [eV] [eV] [A] [A]

12 H 3C-CHr CH 3 290.6 291.6 300.0 1.0 9.4 [8.38] 1.532(3)

H 3C-CH=CH 2 290.7 292.5 301.0 1.8 to.O [8.39] 1.506(3) 1.342(2)
H3C- C=C*H 290.7 310.0 19.0 [8.39] 1.207(5)
H 3C*-C=CH 291.3 292.5 1.2 1.458(5)
H 2 C=C=CH 2 290.5 293.5 309.0 3.0 18.5 [8.4OJ 1.308(1)
H 2 C=CH-CH=CH 2 290.4" 295.5 303.0 5.1 12.6 [8.12]" 1.465(3) 1.345(2)
C6 H 6 290.3 293.8 301.0 3.5 10.7 [8.41] 1.396(1)
14 HO-C*H=O 295.8 296.6 303.5 0.7 7.7 1.358(3)
HO-CH=O* 539.0 547.0 8.0 [8.42, 43] 1.214(3)
HO*-CH=O 540.7 542.1 1.4 1.358(3)
O=C*=O 297.5 314.0 16.5 [8.44] 1.160(0)
O*=C=O 540.8 542.0 559.0h 1.0 18.0h [8.45]i 1.160(0)

• Sum of atomic numbers of bonded pair.

b The excited atom is indicated by an asterisk.
C For a tabulation ofIPs, see [8.46).

d For a tabulation of bond lengths, see [8.37, 47).

• Estimated.
f See also Fig. 6.23.

" See also Fig. 6.15.

h This assignment is questionable, see Fig. 8.18.
i See also Fig. 6.24.

[8.50, 51] shortly thereafter. These authors introduced the term hyperconjug-
ation and attributed it to a n-like interaction ofthe terminal CH 3 group with the
p-orbital(s) on the central Sp2_ or sp-hybridized carbon atom. This is easily
visualized from the bonding MOs for NH3 shown in Fig. 3.3, which can be
viewed as two n-like orbitals (Ie), perpendicular to the molecular symmetry axis,
and two O'-like orbitals (3a 1 and 2a 1 ), along the symmetry axis. The specific case
for the H3C- group with C 3v symmetry is shown in Fig. 8.12, where the open
bond goes to another C atom, for example. The antibonding MO on the CH 3
group (Sp3 hybrid) associated with the C-C bond is marked O'~c in Fig. 8.12 and
belongs to the a 1 representation in C 3v symmetry. This MO gives rise to the
dashed resonances in Fig. 4.17. The MOs associated with the C-H bonds are
two "n*" (e) orbitals and one 0'* (a 1 ), also shown in Fig. 8.12. These orbitals give
rise to resonances B and A, respectively, in Fig. 4.17. In propene and methyl-
acetylene the filled "nCH" HOMOs shown at the bottom of Fig. 8.12 interact
with the p-orbital(s) of the central carbon atom to shorten the C-C "single"
bond.
A different and seemingly simple explanation for the shortening of the
"single" bond in alternating hydrocarbons has been given by Walsh [8.53] and
Coulson [8.54]. Since the mean radius of an atomic 2s orbital is smaller than that
of a 2p orbital, the effective radius of an spx orbital should increase with x. Bonds
 8.5 Correlation for Large Molecules 257

Fig.8.12. Schematic molecular orbitals of the -CH3 group [8.52].

The filled circles indicate hydrogen (smaller) and carbon (larger). For
each MO the atomic constituents are shown and the orbitals are
labelled 1t or u, which refers to the symmetry relative to the 3-fold axis
and the nature of the bond, and, in brackets, by the irreducible
representation in C 3 , symmetry. The highest occupied MO (HOMO)
shown at the bottom, labelled 1tCH (e), is C- H bonding in nature. The
other three orbitals are anti bonding and unfilled and transitions to
these orbitals are seen in the spectra in Fig. 4.17 as resonances A (U~H)'
resonances B (1t~H)' and the dashed resonances (u~cl, respectively. The
hyperconjugation effect arises from the interaction of the filled 1tCH (e)
orbital with a p orbital on an sp- or sp2-hybridized carbon atom,
attached on the "open" bond

yy
"CH (e)

formed by sp3-hybridized atoms (75% p-character), should be longer than those

of an sp2-hybridized atom (67% p-character) and those in turn should be longer
than those formed by an sp-hybridized carbon atom (50% p-character). This
simple model, in fact, makes some quantitative predictions. One would expect
the contraction to be roughly half as large on going from propane
(H 3C-CH 2-CH 3 ) to propene (H 3C-CH=CH 2) as from propene to methyl-
acetylene (H 3C- C=CH), in excellent accord with the observed contractions
0.026 A and 0.048 A (Table 8.1). It is interesting to note that this trend is also
followed by the difference flR = 0.068 A between the "single" bond lengths
in butane (H 3C-CH 2-CH 2-CH 3) and butadiene (H 2C=CH-CH=CH 2) and
flR = 0.089 A between butadiene and diacetylene (HC=C- C=CH).
However, in this case there is a clear contribution from n-conjugation, i.e.,
interaction of the p-orbitals on the central two carbon atoms.
Whatever its origin, the C-C single bond shortening in propene and
methylacetylene should lead to a higher-energy shift of the (1t-c resonance in
these molecules relative to ethane. In contrast, the C=C and C=C (1* resonances
associated with the double and triple bonds in these molecules are expected to
fall at the same positions as in ethylene and acetylene, respectively. This is
indeed observed in the gas phase ISEELS spectra of these molecules (Fig. 8.13);
the peak positions are summarized in Table 8.1. In propene the C-C (1*
resonance falls at 292.5 eV, 1.3 eV higher than in ethane (Table 4.2), the magni-
tude of the shift being close to that (1.5 eV) expected for the 0.027 A shortening of
the C-C single bond in propene. The shift of the C-C (1* resonance for
258 8. u* Resonance Position and Bond Length

Fig.8.13. Gas phase ISEELS spectra of ethylene

(H 2 C=CH 2 ) [8.55], propene (CH 3-CH=CH 2 )
[8.56], ethane (H3C-CH3) [8.38], methylacetyl-
ene (CH 3-C=CH) [8.56], and acetylene
(HC=CH) [8.56]. The observed positions for the
single (Ut-d, double (ut~d, and triple (Ut"d
bond resonances are indicated. For methylacetyl-
ene the observed C-C 0'* resonance position is
lower than that expected from Fig. 8.7 for the
":J 1.46 A length of the "single" bond, which is mar-
ked by an arrow. Peaks arising from muItielectron
excitations are shown shaded. Calculated spectra
* for the same molecules are shown in Fig. 6.14
°c=c

IH 3 C-C=CH
"'-----

J
X 2" :

!, _ _ _--:...-:.H,C=CH

1 '
x"4 C-H*
280 290 300 310 320
Excitation Energy (eV)

methylacetylene, however, although qualitatively in the right direction, is too

small for the significant bond length shortening of 0.075 A relative to ethane.
The position found for the O't-c resonance in methylacetylene is thus too low in
energy relative to that expected for the 1.46 A bond length, marked by an arrow
in Fig. 8.13. This indicates a limitation in the quantitative use of the building
block picture for bond length determinations in larger molecules.

8.5.2 Non-aromatic Hydrocarbon Rings

In the following we would like to extend the discussion of the previous section to
cyclic hydrocarbons. For the time being we shall limit our discussion to
saturated rings and rings with some unsaturated bonds and specifically exclude
strongly conjugated or aromatic rings. These will be discussed in the next
section. We shall sequentially discuss saturated rings, rings with only one double
bond, and rings with alternating single and double bonds. The relevant spectra
are taken from the work of Hitchcock et al. [8.57].
As discussed in Sect. 6.4.3, saturated rings, in principle, are O'-conjugated and
the interaction between the adjacent single bonds in these structures is expected
to lead to a splitting of the u* resonances. Indeed, the spectra of saturated
hydrocarbon chains and rings exhibit a splitting of the u* resonances expected
from theory, but the higher-energy u* resonance is very weak, as is evident from
the spectra in Fig. 6.19. In practice, one may thus ignore the second weak u*
 8.5 Correlation for Large Molecules 259

resonance and simply use a one-to-one correlation between the prominent

lower-energy (1* resonance around 292 eV and the C-C single bond in the
molecules, as expected from the building block picture. This works reasonably
well for the larger rings as shown in Fig. 8.14. Here we have plotted the region of
the (1* resonances only, after subtraction of a smooth continuum background.
Except for the smallest ring, cyclopropane, the observed positions of the
prominent (1* resonances are within 1 eV of those marked by an arrow in
Fig. 8.14, predicted by Fig. 8.7 for the respective C-C bond lengths. For cyclo-
propane, the disagreement may originate from the strain in the molecule, caused
by unusual bond angles and bond-bond interactions between adjacent bonds.
This conclusion is supported by the close agreement of the (1* resonance
position for normal propane and that of the longer hydrocarbon chains
(Fig. 6.19).

Energy Relative to IP (eV)

0 10 20 3

u' Resonances 2

1.51A

~ C3HS
5
0 0
2" 4
·c
:::l

.c 3
0 .e 2
~
·iii
c:
'"
C
3 0
CsH,o

0 0 2

,
310
Excitation Energy (eV) Excitation Energy (eV)

Fig.8.14. Gas phase ISEELS spectra of cycloalkanes in the region of the u* resonances after
subtraction of an estimated background corresponding to the non-resonant continuum [8.57]. The
expected resonance positions in the building block picture, according to the listed C-C bond lengths
and use of Fig. 8.7, are marked by arrows

Fig.8.15. Gas phase ISEELS spectra of cyclopentene (CsHs), cyclohexene (C6 H IO ), and cycloocta-
tetraene (CsHs) [8.57]. We have indicated the positions of the respective IPs by a dashed line and
marked by arrows the single and double bond u· resonances expected from the listed bond lengths
by use of Fig. 8.7, i.e., from the building block picture
260 8. u· Resonance Position and Bond Length

Figure 8.15 displays the spectra of two unsaturated rings, cyclopentene

(CSHB) and cyclohexene (C 6 H lO ), which each have one double bond and several
adjacent single bonds. In addition the spectrum of the well-known ring cyclo-
octatetraene (CBH B) is shown, which despite its formally alternating bond
structure has minimal conjugation because of its nonplanar geometry. In all
cases the spectra exhibit two well-defined resonances above the IP which can be
associated with u* resonances due to the C-C single and C=C double bonds in
the rings, respectively.
The assignment of the two observed resonances in the cyclopentene and
cyclohexene spectra to the single and double bonds in the molecules, respect-
ively, is confirmed by a direct comparison of the spectra of cyclopentane and
cyclopentene, and of cyclohexane and cylcohexene, shown in Figs. 6.19,8.14 and
8.15. Clearly the higher-energy (double bond) u* resonance near 296eV for
cyclopentene is shifted relative to the 294eV shoulder in the cyclopentane
spectrum and it is much more pronounced. For cyclohexene an enhanced
structure near 298 eV is found relative to a weaker structure centered slightly
higher in cyclohexane.
The qualitative correlation between the single and double carbon--carbon
bonds in the rings and the u* resonances in the spectra, however, cannot be used
for accurate bond length determinations, at least not by application of the rules
derived from the spectra of simple hydrocarbons. This is indicated by the
disagreement between the observed resonance positions in Fig. 8.15 and the u*
resonance positions, shown as arrows, predicted from the indicated bond
lengths and the correlation diagram in Fig. 8.7. The best agreement exists for the
C-C single bonds in cyclopentene and cylcohexene, while in the other cases
observed and predicted positions differ by as much as 4eV. For cycloocta-
tetraene the disagreement may be smaller than indicated by Fig. 8.15, because
the observed resonance near 292eV may partly be a shake-up structure associ-
ated with the n* resonance, as indicated by polarization-dependent spectra of
CBH Bon Pt(111) [8.57]. The true C-C single bond resonance in the chemisor-
bed spectrum falls near 293 eV, within 1 eV of the predicted position. Again, as
for the case of unsaturated chain-like hydrocarbons, we find limitations in the
quantitative prediction of bond lengths by use of the building block picture in
unsaturated hydrocarbon rings.

8.5.3 u-Conjugated and Aromatic Molecules

As discussed in Sects. 6.4.3 and 6.4.4, u-conjugated molecules exhibit more than
one u* resonance yet are typically characterized by a single bond length. The
question arises whether a correlation exists between the bond length and one or
both of the resonance positions. Since the splitting arises from first-order
interactions between originally degenerate orbitals (Fig. 3.5), it appears that
such a correlation should exist and that it should involve some "average" u*
resonance energy. Another question is whether the "average" resonance energy
 8.5 Correlation for Large Molecules 261

is given simply by the arithmetic mean of the positions or whether the relative
intensities of the two peaks need to be folded in.
The results for saturated hydrocarbon rings discussed in the previous section
indicate that it is the intensity weighted center of gravity of the (7* resonances
which exhibits a correlation with the bond length. In these systems the weakness
of the higher-energy resonance would cause the center of gravity to lie close to
the position of the dominant lower-energy resonance, in accordance with the
correlation indicated in Fig. 8.14. A similar conclusion is also obtained from the
spectra of chain-like hydrocarbons, as illustrated at the top of Fig. 8.16a for
propane. Here the average of the two observed resonance positions is clearly
much higher than the expected position, marked by an arrow, for the known
1.53 A bond length. On the other hand, the center of gravity of the two

Fig. 8.16. (a) Splitting of the (J* reson-

ances for the molecules (from top to bot-
tom) propane, propene, allene, and ben-
zene. In propene the two C-C bond
lengths are indicated and the (J* resonance
positions agree with those predicted from
the data for "diatomic" hydrocarbons
(Fig. 8.7). The C-C bond length in the (J*
conjugated molecules propane, allene and
benzene is also given and the correspond-
ing (J* resonance position, predicted by the
building block picture, is indicated by an
arrow. The observed resonance splitting
around this value caused by conjugation is
indicated. (b) (J* resonance position versus
C-C bond length. The solid line is taken
from Fig. 8.7, except that the absolute (J*
resonance energy scale (right ordinate) has
280 290 300 310 320 been shifted by 0.5eV to place the average
Excitation Energy (eV) IP at 290.5 eV, instead of 29 1.0 eV. This
corresponds more closely to the average IP
%
-, 20 310 ~ of the molecules in (a). The data for pro-
4
, pene fall exactly on the solid curve for the
UJ
305 >: "diatomic" hydrocarbon building blocks.
e>
Q) The conjugated molecules exhibit a split-
300 ofi ting of the (J* resonances around this
Q)
o curve. Note that for propane the higher
295 ~
I:
o energy resonance around 300eV is very
"'
Q) weak and the center of gravity is thus close
290 a:
to the lower energy resonance (compare
1.2 1.3 1.4 1.5 Fig. 6.21) and is close to the solid correla-
Bond Length, R (..8.) tion curve in (b)
262 8. (J* Resonance Position and Bond Length

resonances falls close to the lower energy peak and therefore near the expected
position (arrow).
The second spectrum shown in Fig. 8.16a is that of propene and, as discussed
in Sect. 8.5.1, in this case the observed and predicted positions agree with the
building block picture. This is seen directly from Fig.8.16b, where the two
positions of the 0'* peaks for propene (solid circles) fall on the solid curve taken
from Fig. 8.7 for the pseudo-diatomic hydrocarbons.
A good example of the effect of a-conjugation is allene (H 2 C=C=CH 2 ), see
Sect. 6.4.3 and also Fig. 6.23. Its gas phase spectrum, recorded by Sodhi and
Brion [8.58] and shown in Fig. 8.16, exhibits two 0'* resonances whose center of
gravity closely agrees with the position, marked by an arrow, predicted from the
1.31 Abond length. In this case the two 0'* resonances have approximately equal
intensities (areas), which is better seen from the spectrum of allene on Ag(110)
shown in Fig. 6.23. As shown in Fig. 8.16b, the two resonance positions are
almost symmetrically located around the solid correlation line for the pseudo-
diatomic hydrocarbons. Finally, the much discussed spectrum of benzene [8.41,
59, 60] also follows this trend as shown in Fig. 8.16. As for allene the two 0'*
resonances lie nearly symmetrically on both sides of the position expected from
its 1.40 A bond length.
The splitting of the 0'* resonance in allene has been studied in more detail by
means ofXa-MS theory by Wurth and Stohr [8.61]. Their spectra calculated for
the ground state geometry are shown in Fig. 6.23. Although the calculated
splitting (11 eV) of the 0'* resonance is somewhat smaller than the measured
splitting (16eV) there is good agreement between the overall structures in the
experimental and theoretical spectra. Wurth and Stohr also calculated spectra at
non-equilibrium distances to elucidate the distance dependence of the 0'*
resonance positions. The results shown in Fig. 8.17 show a nice correlation
between the change of the two 0'* positions for modified allene (solid data points
and lines) and that calculated for the change of the 0'* position between

~ 25
>
.!!!.
~ 20
.2
15
~
<:
:2'0; 10
0 Fig.8.17. Positions of the (J* resonances in
D..
Q) 5 allene (solid circles and lines) as a function
0
<: of the carbon~arbon bond length, calcu-
as
<:
0 0
lated by means of XIX-MS theory [8.61].
III
Q) The ground state bond length is 1.308 A.
a:
The calculated positions for acetylene, eth-
'b -5
ylene, and ethane are shown for compari-
1.2 1.3 1.4 1.5 son as open squares, connected by a da-
C-C Bond Length (.8.) shed line
 8.5 Correlation for Large Molecules 263

acetylene, ethylene, and ethane (open squares and dashed line). As the bond
length in allene is shortened below the 1.31 A ground state value, the average
energy of the two u* resonances moves higher, as expected, and the splitting
becomes larger. This latter effect is expected because of the bond overlap
arguments presented at the end of Sect. 4.3 in connection with Fig. 4.18. For
larger than ground state distances in allene the average u* energy decreases and
the splitting is reduced, as expected.
Finally, we shall discuss CO 2 , a molecule that is strongly u-conjugated like
allene. The C and 0 K -edge spectra are given in Fig. 6.24; here we want to take a
closer look at the correlation between the two u* resonance positions in the 0
K-shell spectrum and the carbon-oxygen bond length (Table 8.1). The splitting
ofthe u* system in the 0 K-shell spectrum, observed experimentally by ISEELS
[8.44, 56] and calculated by means of the Xa-MS method [8.62], is shown for
clarity again in Fig. 8.18, this time in comparison to CO. The bond length in CO
(1.13 A) is only slightly smaller than that in CO 2 (1.16 A), and one would
therefore expect the center of gravity of the two CO 2 u* resonances to be about
1 eV lower, relative to the respective IPs, than in CO.
The experimental and calculated u* energies relative to the IP taken from
Fig. 8.18 are plotted in Fig. 8.19 as a function of bond length. Experimental data
points for CO 2 are indicated as filled circles, calculated ones by open squares.
The solid line and filled circles on the line are taken from Fig. 8.8 and represent
the experimental data for C=O, H 2 C=O, and H3C-OH, and the dashed line and

Experiment Xa-MS Theory

s-'c a*
co CO
I
1 IP
:::J

~
~ x-
~ 2
:c
.e
~
'iii
c:
Q)
C
a
l1
'*
Ia 21'*
I I

IP : : CO 2 CO 2
I I, II

II
I
I
B

530 540 550 560 570 530 540 550 560 570
Electron Energy Loss (eV) Excitation Energy (eV)
Fig. [Link]. Illustration of the splitting of the u* resonance in CO into two resonances ut and u! in
CO 2 , Left: Experimental IS EELS spectra of the free molecules at the 0 K-edge [8.44, 56,63]. An
ambiguity in the assignment of the u~ resonance is indicated by the two dashed lines, marking the
positions of two resonances A and B. Right: Spectra for the same two molecules calculated by means
of the XIX-MS method [8.62] (see also Fig. 6.24). The resonances in the calculated spectra are labelled
by the irreducible representations of the unfilled MOs associated with the transitions
264 8. 0'* Resonance Position and Bond Length

Fig. 8.19. Correlation of 0'* resonance positions

o=c=o
18
'B o K-edge
-O-Xa-MS Theory
cules. Experimental data points for the °
with the C-O bond lengths in a variety of mole-
K-
~ 16 edge excitation in CO, H 2 CO, and CH 3 0H,
~ - e - Experiment taken from Fig. 8.8, are shown as solid circles,
e:: 14 connected by a solid line. The data points mar-
ked with open squares and connected with a
.s 12
dashed line are calculated values by means of
~ the Xa-MS method [8.62]. The corresponding
c: 10
o
:;::;
spectra are shown in Fig. 4.5. At a bond length
.~ 8 of 1.16A we also show experimental (solid cir-
Q. cles) and calculated (open squares) values for the
fl
c:
6 two 0'* resonance positions in CO 2 , taken from
til
c:
Fig. 8.18. The points labelled A and B corres-
o 4 pond to the 0'* resonances with the same labels
8l in Fig. 8.18
a:
'b
o
-2
1.1 1.2
C-O Bond Length (A)

open squares on the line are calculated (1* resonance positions for the same
molecules (Fig. 4.5).
There is a nice correspondence between the calculated center of gravity for
the (1* resonances in CO 2 and the dashed correlation line for the diatomics and
pseudodiatomics. As for allene and benzene in Fig. 8.16, the two (1* resonances
are nearly symmetrically split about the correlation line. The situation for the
experimental CO 2 spectrum is less clear since, as indicated in Fig. 8.18, the
experimental assignment is not completely clear with respect to the location of
the higher energy (1! resonance. Two peaks, labelled A and B, are observed, and
it is likely that the true (1* resonance in this region is masked by shake-up peaks.
Unfortunately, at the time of writing no polarization-dependent NEXAFS
spectrum of oriented CO 2 on a surface is available. As shown in Fig. 8.19, peak
A is closer to the expected position for the (1! resonance. Future measurements
will have to show whether this prediction is correct.

8.6 Extension to Condensed, Physisorbed,

and Chemisorbed Molecules

For free molecules we have established correlations between the intra-molecular

bond lengths and either the absolute (1* resonance position or the relative
resonance position with respect to the Is IPs. In establishing similar relation-
ships for molecules with extra-molecular interactions, such as van-der-Waals or
chemical bonds, we need to understand how the resonance positions are
 8.6 Extension to Condensed·, Physisorbed, and Chemisorbed Molecules 265

influenced by these extra-molecular effects. We briefly addressed this problem at

the beginning of Chap. 6, but here we wish to be more quantitative.

8.6.1 Chemical Shifts and Resonance Positions

The influence of extra-molecular bonds on the IP has been well studied by
photoemission techniques [8.64-67]. Let us for the following discussion assume
that the Is IP or binding energy is determined by the position of the "main peak"
in the photoemission spectrum relative to the vacuum level. In a simplified
model there are two main effects which may cause a change in the Is binding
energy. First, charge transfer due to a change in the bonding interaction of a
given atom or molecule in the ground state may lead to a core level binding
energy shift, a so-called initial-state-bonding shift or bonding shift, for short.
Secondly, the charge polarizability of external ligands may lead to different
shielding or screening contributions of the core hole. The corresponding shift in
the IP is referred to as a final-state-relaxation shift, or simply relaxation shift. In
practice, their separation is often difficult and the experimentally measured shift
between two atoms or molecules is therefore simply called a chemical shift [8.65,
67]. Below we shall also use this terminology, but we shall assume that in a given
case we can distinguish the bonding from the relaxation component of the total
chemical shift. In theory such a separation is possible, since initial-state-bonding
shifts are given by the change in Koopmans' eigenvalues (Sect. 2.4), while
final-state-relaxation effects refer to the separation of the main line from the
Koopmans' value.
Understanding the influence of the bonding and relaxation components of
the chemical shift on the resonance energies measured in NEXAFS is the central
problem in extending the bond length correlation from free to chemisorbed
molecules. We can start by addressing this problem by systematic investigations
of a series of free molecules which have been chemically modified to induce
either a bonding or relaxation shift without a significant change in bond length.
For such systems, one can therefore hope to separate out the effect of bonding
and relaxation shifts on the n* and/or 0"* resonance positions.
The effect of initial-state-bonding shifts on the resonance positions is most
clearly revealed by Fig. 4.15, where the C Is IP increases by 5.1 eV in going from
H 2C=O to F 2C=O. As identified in the early work of Siegbahn et al. [8.64],
substitution of hydrogens by electronegative ligands like fluorine causes large Is
binding energy shifts, which can be largely attributed to electrostatic effects in a
ground state picture. This has been studied in detail in conjunction with K-shell
excitation spectra by McLaren et al. [8.55] (see also Fig. 4.16) and Robin et al.
[8.68].
For the aldehydes shown in Fig. 4.15, the C=O bond length changes by a
total of 0.04 A, from 1.21 Ain H 2C=O, 1.18 Ain FHC=O to 1.17 Ain F 2C=O.
According to Fig. 8.6 the 0.04 Achange in c-o bond length is expected to cause
a relatively small 1.1 eV shift ofthe 0"* resonance relative to the IP. This is borne
out by Fig. 4.15, where the 0"* resonance is seen to lie around 6 ± 1 eV above the
266 8. u* Resonance Position and Bond Length

Bonding and Relaxation Shifts at Constant R Fig. 8.20. Schematic energy level dia-
Bonding Shift Relaxation Shift gram illustrating the effects of bonding
(del and relaxation (d R ) shifts on the Is
J IPs and on bound (n*) and continuum
(u*) resonance positions. Note that
Vacuum bonding shifts affect both the Is IP and
Level the absolute resonance energies ap-
rr' proximately equally, while relaxation

IP C lc
rr
EC
u
IIP,1 rr
E'
u
shifts affect the IP but not the absolute
resonance energies

IP, in all three cases. Thus this example shows that for a series of molecules with
nearly constant bond length but large changes in the IP, the absolute u*
position, E", moves with the IP. This is equivalent to the statement that the
relative u* position, L\", is to first order independent of initial-state-bonding shifts.
These results are summarized in the form of a schematic energy level
diagram in Fig. 8.20. Here we have simply indicated the energy positions of the
Is orbital and n* and u* MOs relative to the vacuum level for a hypothetical
molecule such that the IP and the transition energies, E" and E", are given by the
relevant energy differences. Note that although the shift L\c in the diagram is
caused by a change in initial state bonding, the energy levels reflect the final state
energetics, relevant in K-shell photoemission and X-ray absorption. In the
presence of a bonding shift, L\c, which may have a positive or negative sign, the
transition energies all follow the change in the IP. Hence, in this picture, the
positions of the n* and u* orbitals relative to the vacuum level remain fixed.
The case of a final-state-relaxation shift has also been implicitly dealt with
before in Fig. 6.1. Relative to free CO, the C Is IP in Mn 2 (CO)10 falls at a 2.8 eV
lower binding energy. This shift has been shown by Plummer et al. [8.69, 70] to
arise predominantly from a relaxation effect. This conclusion was reached by
carefully determining the centers of gravity (intensity-weighted average of
energies) of the "main peak" and of all other multielectron photoemission peaks
for CO and a variety of carbonyls. They were found to be identical within
experimental uncertainty (± 0.5 eV), as demanded by the Manne-Aberg sum rule
(Sect. 2.5.3), in the absence of any initial-state-bonding shifts. Despite the 2.8 eV
shift of the IP between CO and Mn 2 (CO)10' the u* resonance shifts by less than
1 eV to lower binding energy. This small shift can be mostly explained by a slight
lengthening of the C-O bond in Mn 2 (CO)10 (1.130(4)A [8.71]) relative to that
in free CO (1.128(5)A). Thus we- conclude that, to first order, relaxation shifts
affect only the IPs and not the K-shell transition energies.
This important fact was first pointed out by Stohr and Jaeger [8.72] in their
early NEXAFS study of diatomic molecules on Ni(lOO). Since then this has been
 8.6 Extension to Condensed, Physisorbed, and Chemisorbed Molecules 267

verified in many other cases, like the high resolution study of the n* resonance
position for free and condensed CO, and CO chemisorbed on Ni(111) by Jugnet
et al. [8.73] and the ISEELS study of various carbonyls by Riihl and Hitchcock
[8.74, 75].
The effect of relaxation is also illustrated by an energy level diagram in
Fig. 8.20. In the presence of a relaxation shift, A R , both the 1s and n* and 0'*
levels change their position relative to the vacuum level, leaving the transition
energies invariant. The insensitivity of the resonance positions to relaxation can
be explained by the fact that the molecule remains neutral in the 1s -+ n* and
1s -+ 0'* excitation processes. Even in the case of the 0'* excitation the excited
electron remains trapped long enough to self-screen the core hole. Hence
changes in the polarizability of the environment, which give rise to A R , are
insignificant to first order. In contrast, in the photoemission process the mole-
cule is ionized and the core hole screening depends on the polarizability of the
environment. Since resonance energies follow bonding but not relaxation shifts,
K-shell excitation spectra may in fact be used to separate bonding from
relaxation shifts. This point has not been appreciated in the literature.
The conclusion from the above discussion is that for the consideration of
resonance energies we only need to worry about bonding shifts in going from
free molecules to molecules in the environment of a polarizable medium, e.g.,
solid molecular layers, or physisorbed or chemisorbed molecules. This is a very
important and powerful result and we shall use it below to develop schemes for
the determination of bond lengths in adsorbed molecules. We shall consider
three fundamental molecular adsorption cases on surfaces, and then conclude
with some general remarks in the last section.

8.6.2 Weakly Adsorbed Molecules

First, we assume that the molecule is in touch with the surface without strong
overlap and mixing of molecular orbitals. In practice, this case corresponds to
physisorption, i.e., van-der-Waals bonding. This type of bonding is also encoun-
tered in condensed molecular layers (Sect. 6.1.1). In this case the predominant
effect on the 1s IP will be caused by a change in relaxation [8.66], owing to the
possibility that the core hole can be screened better by the availability of an
additional electron reservoir, consisting of the metallic surface or the polarizable
dielectric layer. Because there is no real chemical bonding there will be little or
no electron transfer between the molecule and the environment in the ground
state. Hence bonding shifts and bond length changes, which would arise from
electron transfer out of occupied bonding or into unoccupied anti bonding
orbitals, will be absent to first order. No change in the resonance positions
relative to the gas phase is expected.
This is indeed exemplified by many of the spectra presented earlier. For
example, Fig. 6.10 compares the spectra of free, condensed and weakly chemi-
sorbed CH 3 CN. In all cases the bond length is expected to be almost identical
because of the weak extra-molecular interactions. Despite the fact that a
268 8. a* Resonance Position and Bond Length

Ag(100)
\~----r---"" HC=CH
E

280 290 300 310 320 280 290 300 310 320
Photon Energy (eV)

Fig.8.21. Polarization dependent NEXAFS spectra at (a) normal and (b) grazing X-ray incidence
for ethylene (HzC=CH z) on Ag(110) [8.76], propene (CH 3 -CH=CH z) on Ag(110) [8.76], ethane
(H 3 C-CH 3) on Cu(IOO) [8.30], methylacetylide Z (CH 3 -C=C-) on Ag(110) [8.77], and acetylene
(HCECH) on Ag(IOO) [8.78, 79]. The molecules are arranged from top to bottom as in Fig. 8.13 and
the labelling of the resonances is also the same. Note the close correspondence between the a*
resonance positions in the two figures. From the polarization dependence of the spectra the
molecules are seen to lie down on the surface, in all cases

relaxation shift in the C Is IPs is expected, especially when the molecule is

bonded to the Ag(llO) surface, all resonance positions remain nearly unaffected.
The reason is that bonding shifts are small or negligible. Similar results are also
obtained for butadiene (Fig. 6.15) and benzene (Fig. 6.28). Other examples are
given by the spectra of gas phase O 2 and condensed and physisorbed O 2 on
Pt(I11), shown in Fig. 7.18, and the spectra of free N2 and N2 weakly chemi-
sorbed on Fe(I11), shown in Fig. 7.19.
Hydrocarbons typically adsorb weakly on noble metal surfaces, and several
examples are shown in Fig. 8.21. From the polarization dependence it is obvious
that in all cases the molecules are n-bonded to the surface, with their
carbon-carbon bonds approximately parallel to the surface. With the exception
of methylacetylene, which is actually present on the surface as methylacetvlide 2
(H3C-C=:C-), the narrowness of the n* resonance and/or the low desorption
temperatures indicate weak chemisorption for the cases shown. The molecules

2 Methylacetylide was prepared by exposing the Ag(110) surface, precovered with 1/3 monolayer of
atomic oxygen, to a saturation dose of methylacetylene at 90 K and annealing to 250 K.
 8.6 Extension to Condensed, Physisorbed, and Chemisorbed Molecules 269

are arranged in the same order from top to bottom as the gas phase analogues in
Fig. 8.13, and comparison of the two figures reveals an almost quantitative
correspondence between the n* and 0'* resonance positions in the spectra of the
respective free and chemisorbed molecules.
Hence, for molecules weakly bonded to surfaces we can use the same
correlation between absolute 0'* energy position, Ea , and bond length, R, as for
the gas phase.

8.6.3 Strongly Adsorbed Molecules Without Bonding Shifts

As the second case we assume that upon adsorption on the surface a strong
chemical bond is formed and that the interaction of molecular orbitals and
orbitals on surface metal atoms leads to some synergetic transfer of electrons
from filled MOs to the metal and back from the metal into unfilled MOs, as
discussed for CO and C 2 H 4 in Sect. 6.1.1. This electron transfer affects the
relative occupation of bonding and anti bonding MOs and therefore may change
the bond length considerably, yet the overall charge on the molecule may
remain nearly unchanged. Thus we can imagine the case of a chemisorbed
molecule with a significantly different bond length from the gas phase without a
significant Is bonding shift. Strong relaxation shifts are again expected [8.66]
but should have no effect on the resonance positions. The 0'* resonance should
therefore exhibit a shift arising from the change in bond length alone. The n*
resonance position is expected to be largely unaffected because it is insensitive to
bond length changes, to first order. Note that the intensity and width may
change, however.
In practice, this case is encountered for hydrocarbons, as first discussed by
Stohr et al. [8.13] in their study of hydrocarbons on Pt(111). As shown in
Fig. 8.7, free hydrocarbons have remarkably similar Is IPs (290.8 ± 04eV).
Upon chemisorption, the Is IP relative to the vacuum level (obtained by
adding the work function to the XPS binding energy, measured relative to the
Fermi level) is lowered by only about 1 eV, resulting from a small bonding shift
( < 0.5 eV) and a relaxation contribution [8.13].

Because of the small bonding shifts for gas phase and chemisorbed hydrocar-
bons, it is again possible to use the gas-phase correlation between the absolute
resonance position, Ea , and the bond length, R. This approach was first utilized
by Arvanitis et al. [8.30].
For a given surface with work function 4J, this scheme is equivalent within
errors of about ± 0.5 eV to that originally used by Stohr et al. [8.13]. These
authors established a separate correlation for chemisorbed molecules involving
the relative resonance position referenced to the Is binding energy relative to the
Fermi level. Because of the small bonding shifts this curve is simply offset by a
constant amount, 4J + leV [~7eV for Pt(111)], from the corresponding gas
phase correlation between the relative resonance position Ila and the bond
length R shown in Fig. 8.7.
270 8. u* Resonance Position and Bond Length

.~ (a) (b) E
u*
c:
::l
4 ....
...
.ri
~
"0
Qi
:;:
c:
...o
"0
Q)
iii
iii
:eco
0.

280 290 300 310 320280 284 288 292

Photon Energy (eV)

Fig.8.22. NEXAFS spectra of chemisorbed ethylene on various metal surfaces, Ag(lOO) [8.78],
Ag(llO) [8.76], Cu(lOO) [8.30, 78], and Pt(lll) [8.80], recorded at (a) normal X-ray incidence and
(b) 20° grazing incidence. At the bottom the gas phase IS EELS spectrum [8.55] is shown for
comparison. In all cases the molecule lies down such that the u* resonance is most pronounced at
normal incidence and the n* resonance at grazing incidence. The shift of the u* position to lower
energy and the broadening of the n* resonance in going from a Ag to a Pt substrate indicate
strengthening of the molecule-substrate and weakening of the intra-molecular C=C bond

A beautiful example, Fig. 8.22, reveals how the NEXAFS spectrum of free
ethylene (C 2 H 4 ) changes as the molecule is successively more strongly bonded
to various metal substrates [8.81]. The spectra are arranged such that from
bottom to top the interaction with the metal surface increases, as independently
confirmed by the desorption temperatures: ~ 150 K for Ag(100), ~ 165 K for
Ag(llO), ~200K for Cu(I00), and >300K for Pt(I11). Again the polarization
dependence shows that ethylene lies down on the surface. The increasing
interaction with the surface is reflected both by the broadening of the n*
resonance and the shift in the u* resonance position to lower energy, as
indicated. For Pt(lll) the u* resonance falls at about 293eV, close to that
expected for a C-C single bond.
Following our earlier discussion we have plotted in Fig. 8.23 the gas phase
correlation (solid line and solid circles), taken from Fig. 8.7, and placed the
absolute u* energies, from Fig. 8.22, on this curve (open squares). The
carbon-carbon bond lengths for ethylene on the various substrates can thus be
determined to be: 1.37 Afor Ag(I00), 1.39 Afor Ag(110), 1.44 Afor Cu(I00), and
1.50 Afor Pt(lll). All values should have error bars of about ± 0.04 A, corres-
ponding to an uncertainty in energy of ±2eV.
At this point it is interesting to note that XO(-MS calculations for ethylene on
Pt(lll) [8.82] reveal that the molecule indeed possesses an intra-molecular C-C
 8.6 Extension to Condensed, Physisorbed, and Chemisorbed Molecules 271

20

c),~
310 _
:;- >
~ ~
t
<lb 15 C 2 H4 305 w.
e; on >-
0>
Q;
B 10 c
C H·" Ag(100) 300 W
~ 2 4 D.. O Ag(110)
Q)
u
c c
0
'iii
5 " " Cu(100)
0 295
'"
c
:il
0 ""-. Pt (111) Q)
a::
Il.
0,
'0 '0
0 C 2H6...........
290

1.2 1.3 1.4 1.5

Bond Length, R (iI.)

Fig.8.23. 0"* resonance position versus bond length for acetylene, ethylene, and ethane gas (solid
circles and line), taken from Fig. 8.7, and resonance positions observed for ethylene chemisorption on
various metal surfaces (open squares). The positions of the squares on the line correspond to the
absolute 0"* energies derived from Fig. 8.22 and these positions determine the bond lengths

single bond, and it is di-sigma, not n-bonded to the surface. The origin of the
"n*" resonance in Fig. 8.22b is discussed in more detail in Sect. 10.4.2.
Finally we mention that the same arguments hold in going from a free
hydrocarbon molecule to the corresponding polymer. This is shown by
Fig. 6.12. The spectra of free butene and the polymer polybutadiene are found to
exhibit the same resonance positions because bonding shifts are small ( < 1 eV)
and the C-C and C=C bond lengths in butene and polybutadiene are also nearly
identical.

8.6.4 Strongly Adsorbed Molecules with Bonding Shifts

The third case appears to be the most difficult one, namely, chemisorption of a
molecule with simultaneous change in bond length and net charge transfer. In
this case the IP of the chemisorbed molecule is affected by bonding and
relaxation shifts [8.66] and the resonance positions by bonding shifts and the
change in bond length.
Nevertheless, even in this case a simple correlation may exist. This is best
illustrated by the example of the oxygen, O 2 , and peroxide, H 2 0 2 , molecules
for which a gas phase correlation between a* resonance position and oxy-
gen-oxygen bond length is shown in Fig. 8.9. The bond length difference between
the two molecules is 0.27 A and the a* resonance shift is about 7.5 eV. The IP is
lower in H 2 0 2 by [Link], using the average of the exchange split IPs in O 2
(Fig. 4.14 and Table 4.2). This bonding shift in the IP arises from electron
transfer in H 2 0 2 onto the oxygen atoms, formally yielding an O~ - species.
A physisorbed oxygen molecule on a surface is expected to remain neutral
and the NEXAFS spectrum therefore exhibits a* resonances in the same
272 8. u* Resonance Position and Bond Length

position as in the gas phase, as shown by Fig. 7.18. A strongly bonded O 2

molecule on the surface, on the other hand, is expected to turn into an O~­
species, owing to the large electronegativity of the oxygens and the availability
of conduction electrons. It will therefore assume the same formal valence as in
peroxide, H 2 0 2 , and should thus exhibit the same bonding shift relative to O 2 ,
Therefore, in this case, we should again be able to simply use the gas phase
correlation shown in Fig. 8.9, involving the absolute resonance position Ea. This
example will be discussed in more detail in Sect. 10.3.3. More generally, we
expect that the gas phase correlation involving absolute a* resonance positions
should apply in cases where bond length change and bonding shift upon
chemisorption follow those caused by rehybridization in corresponding free
molecules.
The use of the absolute a* resonance positions is problematic, however, in
the most general case, when the bonding shift of a chemisorbed molecule relative
to the corresponding gas phase analogue is unknown. This is often the case
because the evaluation of such bonding shifts from measurements of the gas
phase and surface binding energies involves the knowledge of the relaxation shift
component and of the work function. In such cases, the position of the n*
resonance may provide a way out, since its position is to first order independent
of bond length changes and relaxation shifts. Hence we can utilize it as an
indicator of bonding shifts, and then use the relative shift of the a* resonance to
evaluate the change in bond length. We shall encounter such a situation in
Sect. 10.2.1 for CO/Pt(111) and CO/Na/Pt(l11).

8.6.5 General Rules, Comments and the Use of Standards

It has become apparent from this chapter that the determination of intra-
molecular bond lengths from NEXAFS spectra usually requires some degree of
chemical insight. This is because valence electron effects in the form of bonding
shifts typically playa role in the energetics of the observed resonances and they
make the establishment of a "foolproof" recipe difficult. As a consequence, bond
length determinations by NEXAFS are usually less reliable and precise than
those by conventional EXAFS, where core scattering phase shifts and Fourier
transform methods can be used.
In practice, it is often necessary and always advisable to consider other
factors besides the a* resonance position in the analysis of NEXAFS spectra.
We have already discussed the importance of the binding energies measured by
XPS, in the last three sections. For unsaturated systems, other information is
contained in the position, width and intensity of the n* resonance. The angular
dependence of the n* resonance yields the molecular orientation, and the
relative intensity and width is a good indication of the strength of the
molecule-substrate bond (backbonding) [8.75]. Finally, the n* resonance posi-
tion gives important information about bonding shifts. When this information is
coupled with that on the a* resonance position additional confidence can be
gained in the analysis.
 8.6 Extension to Condensed, Physisorbed, and Chemisorbed Molecules 273

Correlations between (1* resonance positions and bond lengths, whether

involving absolute or relative resonance positions, are usually most reliable for
diatomics and pseudo-diatomics. We have seen that in larger systems which
follow the building block picture, deviations occur from the simple correlation
established for diatomics and pseudo-diatomics. For (I-conjugated systems the
centers of gravity qualitatively follow the diatomic correlation, yet care has to be
exercised with quantitative distance determinations.
The use of closely related model systems or standards provides the basis for
the most reliable and precise distance determinations. Unfortunately, there is a
shortage of standards for distances in chemisorbed molecules. As mentioned in
the first section of this book, a remarkably small number of structural deter-
minations for chemisorbed molecules have been carried out. Hence, so far we
have had to rely on gas phase spectra and correlations derived from such data as
"standards" for the interpretation of NEXAFS spectra. We shall conclude this
section with two examples of how standards can be used to obtain bond lengths
in chemisorbed molecules without invoking the correlation diagrams estab-
lished for the diatomic and pseudodiatomic gas phase molecules.
The first example is that of the formate (HCOO-) anion on Ag(llO) [8.83],
discussed previously in Sect. 6.4.3 in conjunction with the C K-shell NEXAFS
spectra in Fig. 6.25. These spectra are shown again at the bottom of Fig. 8.24.

Fig. 8.24. Gas phase ISEELS spectra of

methanol (H3C-OH) [8.43, 56J, formal-
dehyde (H 2 C=O) [8.56, 84J, and formic acid
(HO-HC=O) [8.43J in comparison with the
polarization-dependent NEXAFS spectrum
of formate (O=HC=O) on Ag(1l0) taken
from Fig. 6.25 [8.83]. The carbon-oxygen bond
lengths are 1.425 (2) A in H3C-OH, 1.209 (3) A in
H 2 C=O, and 1.214(3)..\ (C=O) and 1.358 (3)
(C-O) in formic acid. The bond length in formate
280 290 300 310 320 is most easily derived by a comparison with
Excitation Energy (eV) formic acid, and is found to be 1.28 A
274 8. u* Resonance Position and Bond Length

Due to bond-bond interactions two 0"* resonances are observed. The curve fits
in Fig. 6.25 indicate that in an angle-averaged spectrum both resonances would
have about equal intensity, and their center of gravity is thus close to 300.0eV.
What carbon-oxygen bond length does this correspond to?
If we use the correlation involving the absolute 0"* position for the C K-shell
case in Fig. 8.8, we obtain a bond length of 1.22 A, close to that in formaldehyde
(H 2 C=O). This is also evident from Fig. 8.24, where we have included the
formaldehyde spectrum for a direct comparison. The considerably different n*
resonance positions (2.5 eV shift) for formaldehyde and formate raises some
doubt, however, whether this approach is appropriate. Furthermore, com-
parison of the gas phase spectra of formaldehyde and formic acid reveals that
the C=O double bond 0"* resonance for formic acid lies about 3 eV higher than
that in formaldehyde, although the bond lengths are nearly the same (1.209 A for
H 2 C=O and 1.214A in HO-CH=O). Therefore the correlation in Fig. 8.8 is not
appropriate for the larger formic acid and formate molecules.
In contrast, we may simply use the spectrum offormic acid (HO-HC=O) as
our standard, from which the formate species is derived. Then the n* resonances
are seen to line up beautifully. Furthermore, the carbon-oxygen bond lengths in
formic acid (Table 8.1) are 1.21 A and 1.36 A, and the two 0"* resonances
associated with these bonds lie symmetrically outside those in chemisorbed
formate. Hence one would expect that the average distance in formic acid,
1.28 A, should be the carbon-oxygen bond length in formate. This value is

Carbon K-edge Oxygen K-edge

1T~_O 1T~_O u~_o

280 290 300 31 0 320 520 530 540 550 560

Photon Energy (eV) Photon Energy (eV)

Fig.8.2S. Angle averaged NEXAFS spectra of carbonate (C0 3 ) on Ag(llO) [8.86] (see also
Fig. 6.26), in comparison with the spectra of bulk cadmium carbonate (CdC0 3 ). The latter spectra
were taken using a single crystal cleaved in air. The agreement of the u* resonance positions indicate
that the carbon-oxygen bond length in C0 3 /Ag(llO) is the same as that in the bulk carbonate
(1.29 A [8.87, 88]) .
 8.6 Extension to Condensed, Physisorbed, and Chemisorbed Molecules 275

indeed remarkably close to that (1.27 ± 0.03 A) typically found in formate

groups bonded to metal atoms [8.47, 85].
Our final example is carbonate (C0 3 ) bonded to Ag(llO). The K-shell
spectra are given in Fig. 6.26. The easiest way to determine the carbon-oxygen
bond length is by comparison of the C0 3 / Ag(llO) spectra to those of a bulk
carbonate (CdC0 3 ). This is done in Fig. 8.25, taken from the work of Madix et
al. [8.86]. Since the n* and CT* resonances align within experimental error, the
bond length in C0 3 on Ag(llO) is 1.29 A, as in CdC0 3 [8.87, 88]. We note that
only the higher-energy CT* resonance (2CT ~ 5e' transition) is observed in the C K-
edge spectrum of carbonate, as previously discussed in conjunction with
Fig. 6.26. The lower component, corresponding to the forbidden 2CT ~ 5a'1
transition, is not observed. This transition would have an approximately 4eV
lower energy as revealed by the 0 K-shell spectrum in Fig. 6.26. Hence, as in the
case of CO 2 , it would be difficult to predict the carbon-oxygen bond length
from the C K-edge spectrum in any other way.
The reliability and precision of intra-molecular bond lengths derived by
NEXAFS will increase in the future with the availability of structural data for
molecules adsorbed on surfaces, obtained with other techniques. In particular,
the availability of enhanced synchrotron radiation sources and soft X-ray
monochromators will allow the recording of SEXAFS spectra with excellent
signal-to-noise levels. It will then be possible to observe the small oscillations
due to intra-molecular scattering (Sect. 6.2.2) and/or determine the geometry
with respect to the surface metal atoms with such precision that the intra-
molecular structure can be inferred. This last approach has already been
pursued by Arvanitis et al. [8.89] for ethylene and acetylene on Cu(lOO).
9. The Angular Dependence of Resonance Intensities

Below we derive the theoretical expressions that govern the angular depend-
ences of NEXAFS resonances in molecular adsorption systems, observed in
polarization dependent studies. A simple, general classification of all molecular
systems is given, and for these classes analytical expressions for the angle-
dependent resonance intensities are derived, assuming that the X-rays are
elliptica:lly polarized.

9.1 Classification of Molecules

For the discussion of the angular dependence of K-shell resonances it is

convenient to classify molecules into general groups. The classification is based
on the concept that bonds and the associated MOs in molecules are highly
directional. Such directionality even exists in chemisorbed molecules although
the overall symmetry of the adsorbate complex will in general be different from
that of the free molecule. As discussed in Sect. 3.6.1, K-shell excitation spectro-
scopy is a localized spectroscopy that probes the amplitude and directionality of
the upper state MOs on the excited atom. It is therefore possible in many cases to
use local symmetry concepts based on the direction of maximum orbital
amplitude on the excited atom relative to the nuclear framework. These con-
cepts are easily understood by consideration of the bonding in unsaturated
diatomics and rings and the resultant spatial distribution of n* and (1* orbitals
[9.1, 2J can serve as the basis for all other cases.
The spatial orientation of n* and (1* orbitals in three classes of diatomics
containing single, double and triple bonds is illustrated schematically in Fig. 9.1.
In reality, of course, these exact molecules do not exist; additional bonds (e.g.,
with H atoms) are needed to satisfy the overall valency requirements. Since
additional bonds to H atoms do not greatly affect the resonances of interest, the
molecules shown in Fig.9.1 are representative of the simple hydrocarbons
ethane (H 3C-CH 3), ethylene (H 2 C=CH 2 ) and acetylene (HC=CH) or the
molecules methanol (H3C-OH), formaldehyde (H 2 C=O) and carbon monoxide
(C=O), respectively [9.1, 3]. Figure 9.1 shows that single-bonded molecules are
characterized by a (1* orbital along the internuclear axis, double-bonded mole-
cules by a (1* and -an orthogonaln* orbital, and triple-bonded molecules by a (1*
and two orthogonaln* orbitals (see also Sect. 3.2). As discussed below, only the
 9.2 Resonance Intensities for Elliptically Polarized X-Rays 277

u' Fig.9.1. Schematic illustration of spatial orienta-

tion of 1t* and u* orbitals in four important

1
Single groups of molecules. Molecules can be divided
Bond into classes depending on whether the 1t* or u*
orbitals point in a specific direction (vector type)
or span a plane (plane type). The angular depend-
ence of the resonance intensities is described by
different theoretical expressions for the "vector"
Double and "plane" cases, respectively
Bond

Triple
Bond

Aromatic
Ring

spatial orientation of the orbital, i.e., the direction of maximum orbital ampli-
tude, determines the angular dependence of the K -shell spectra. Therefore we
can represent a single orbital by a vector, and two orthogonal orbitals by a plane.
In general, a plane is defined by two or more vectors with higher than twofold
rotational symmetry about an axis. This classification leads to the simple
abstract description indicated on the right side of Fig. 9.1.
Figure 9.1 also shows the case of an aromatic ring such as benzene (C6H6) or
pyridine (C s Hs N). In this case the atoms are arranged in a plane and thus the a*
system is characterized by this plane. The n* orbitals can be represented by
vectors perpendicular to the plane. Thus our abstract description in terms of n*
and a* vectors and planes gives a reversed picture for a triple-bonded diatomic
(e.g., CO) and for an aromatic ring (e.g., benzene). In general, then, we need to
consider the angular dependence of the resonance intensities for two cases: (i) n*
and a* vectors and (ii) n* and a* planes. This is done below.

9.2 Resonance Intensities

for Elliptically Polarized X-Rays

The n* and a* resonances of interest here can be described in a molecular orbital

picture as dipole transitions from s initial states to the p component of the n*
and a* final states. The intensity of the resonances I is given by the oscillator
strength f, which is the energy integral of the X-ray absorption cross section ax
27M 9. The Angular Dependence 01 Resonance IntensIties

according to (2.12). In considering the angular dependence of specific resonances

we can assume that the resonance shape will be constant and only their peak
height will change. Therefore, the change in resonance intensity will be propor-
tional to the change in oscillator strength as well as the change in X-ray
absorption cross section, and by use of (2.8) or (2.13) we can write

(9.1)

where e is a unit vector in the direction of the electric field vector E, p is the
momentum operator, Ii) is the Is initial state and If) the molecular orbital final
state of the transition. For elliptically polarized synchrotron radiation from a
bending magnet source the electric field vector E has two phase-related, ortho-
gonal components of different magnitude [9.4]. The larger component lies in the
horizontal orbit plane of the storage ring and the smaller component is vertical.
Let us orient our coordinate system such that the X-rays propagate down the z-
axis and the x- and y-axes with unit vectors ell and e.L lie in the horizontal and
vertical planes, respectively. The electric field is then described by

E = Ell cos(kz - wt) + E.L sin(kz - wt) , (9.2)

where k is the momentum of the X-rays and w is the frequency of the

electromagnetic wave. Ell = IEiliell and E.L = [Link].L are the maximum com-
ponents of the electric field vector in and perpendicular to the electron orbit
plane of the storage ring. Equation (9.2) shows that an elliptically polarized wave
can be viewed as a combination of two orthogonal linearly polarized waves of
different magnitude which are 90° out of phase. As the wave propagates the
electric field vector E rotates and changes its magnitude. It is seen from (9.2) that
the endpoint of E traces out an ellipse, since

(9.3)

and E makes a complete rotation in the x-y plane as the wave advances by one
wavelength. In evaluating the matrix element in (9.1) we need to take into
account all possible orientations of E in the x-y plane since the experiment
averages over many excitation processes. In the dipole approximation the
electric field ofthe photon wave is considered constant over the dimension of the
K-shell, i.e. the wavelength A. is much larger than the K-shell diameter. For the
wave given by (9.2) this means z ~ A./2n = 1/ k and we can therefore set kz = 0
and integrate in time over one wave period. This yields the following expression
for the matrix element in (9.1)

J l<fIE"·pcos(wt) -
2"
E.L ·psin(wt)Ii)1 2 d(wt)
I oc ...:0_----::_ _ _ _ _ _ _ _ _ _ _ _ _ __
(9.4)
J IEll cos(wt) -
2"
E.L sin(wtW d(wt)
°
 9.3 Angular Dependence of the Transition Matrix Elements 279

The cross-terms vanish upon integration and the total intensity is given by

(9.5a)

or

(9.5b)

It is convenient to rewrite (9.5) using a quantity called the degree of linear

polarization or polarization factor P in the plane of the electron beam orbit. 1 P
characterizes the intensity or energy density of the electromagnetic field in the
orbit plane, given by IE"1218n [9.7], relative to the total intensity,

IEII12
(9.6)
P = IEII12 + IE-112 .
P is determined by the X-ray energy and the X-ray optics of the beam line [9.6].
In the soft X-ray region, between 250 and lOOOeV, P is typically between 0.8 and
0.9 for a bending magnet source and ~ 1.0 for an undulator source [9.5]. It
should be noted that the above definition of P also describes the limiting cases of
linearly polarized light, i.e., IE-1 I = 0 or P = I, and circularly polarized light, i.e.,
IE-1 I = IEll I or P = 0.5. With the above definition of P, the total resonance
intensity is given by

(9.7)

9.3 Angular Dependence of the Transition Matrix Elements

In this section we derive expressions for the angular dependence of the matrix
elements in (9.7) for the two cases of final state orbitals discussed in Sect. 9.1, i.e.,
"vector" and "plane" orbitals. For simplicity let us first assume linearly polar-
ized light characterized by the unit electric field vector e. The transition intensity
associated with the matrix element of interest <fle·pli) can be rewritten as

Ioc Ie· <flpli)1 2 . (9.8)

1 P as defined here is plotted in Fig. 5 of the review article by Krinsky et al. [9.5] as a function of X-

ray wavelength for a given storage ring. This definition is preferred by us over the following one:

which is often used in the synchrotron literature, e.g., by Kunz [9.6].

280 9. The Angular Dependence of Resonance Intensities

As discussed in Sect. 3.6.1, for a 1s initial state and a vector final state orbital the
matrix element <flpli) points in the direction of the final state orbital 0, i.e., the
direction of maximum orbital amplitude, and (9.8) assumes the simple form

(9.9)

where the index v denotes the n* or (1* "vector" final state and ~ is the angle
between the electric field vector E and the direction 0 of the final state molecular
orbital (Fig. 9.2). The angular dependence of molecules with n* or (1* planes is
derived by integrating (9.9) over all azimuthal angles in a plane with normal N.
This yields

(9.10)

where E is the angle between E and the normal of the plane N (Fig. 9.3) and the
index p denotes a "plane" final state orbital. Equations (9.9) and (9.10) have been
derived before in Sect. 3.6.1, and in more general terms by Stohr and Jaeger [9.8]
from the expressions governing the electron intensity distribution in angle
resolved photoemission [9.9].
For chemisorbed molecules the transition intensities depend on the orienta-
tion of the electric field vector components Ell and E1- relative to the orientation
of the molecule. The two cases where the n* and (1* orbitals are described by a
vector or a plane, are shown in Figs. 9.2 and 9.3, respectively. As our reference
frame we have chosen the coordinate system (x, y, z) of the elliptically polarized
synchrotron radiation. The X-rays are incident on the sample in the (x, z) plane
which, in practice, is the horizontal plane of the electron orbit in the storage ring.
The dominant component E" of the electric field vector E of the elliptically

z. n

, , I
, 1
1', 1 /
1/1/ '1/
- - - - - - - - -'>vI'

Fig. 9.2. Coordinate system defining the geometry of a u* or 1t* vector orbital on the surface. The
orientation of the orbital, i.e., of the vector 0, is characterized by a polar angle 0( and an azimuthal
angle cpo The X-rays are incident in the (x, z) orbit plane of the storage ring which contains the major
electric field vector component Ell. The X-ray incidence angle (J, which is also the polar angle of Ell,
is changed by rotating the crystal about the y-axis. The weaker component E1. lies in the surface
plane, along the y-axis. The z-axis is the surface normal and the azimuthal rotation axis of the crystal
 9.3 Angular Dependence of the Transition Matrix Elements 281

Z, n Fig. 9.3. The same as Fig. 9.2 for a

n* or u* plane. The plane is charac-
terized by the polar (y) and azi-
muthal (cp) orientation of its normal
N. The plane is tilted from the sur-
face by y

polarized synchrotron radiation lies in this plane [9.6]. It is tilted from the
surface normal by an angle () which is equal to the X-ray incidence angle from
the surface.
In the above discussion we have implicitly assumed that the orientation of
the electric field vector of the incident light remains unaffected by the surface.
According to Maxwell's equations, only the component of E parallel to the
surface is conserved, while the normal component changes in response to the
change in dielectric constant across the vacuum-metal interface, i.e., the X-rays
are refracted. At low photon energies the resulting gradient in the electric field
can indeed be observed as an additional component <!W' EI i) [corresponding
to an additional term rx p' A in (2.6)] in the dipole matrix element [9.10]. It
would cause the perpendicular component E1- to be reduced and the effective
direction of the E vector at the surface to be rotated from that in vacuum. In the
soft X-ray region of interest here, the index of refraction is close to unity, and
refraction and reflection are negligibly small, except at very grazing incidence
angles ( ~ 5°). Hence in NEXAFS the orientation of the E vector of the incident
light is retained at the surface.
In Figs. 9.2 and 9.3 we have only indicated the azimuthal orientation <p of the
adsorbed molecule, without explicitly specifying an azimuthal angle of the E
vector components relative to the substrate. This keeps the theoretical ex-
pressions as simple as possible. In practice, of course, it is the azimuthal
orientation of the molecule relative to the substrate which is the parameter of
interest. This orientation is obtained by establishing the orientation of Ell, which
is always in the horizontal plane relative to the low energy electron diffraction
(LEED) spot pattern of the surface [9.11]. We shall denote the intensities
associated with the angle-dependent matrix elements given by (9.9) and (9.10) for
the Ell component by IU and I~, respectively. The weaker component E1- lies
along the y-axis, which in practice is a vertical rotation axis of the crystal. In
analogy, the angle-dependent intensities for the E1- component are denoted by
I ~ and 1*, respectively. With these definitions (9.7) can be rewritten for the
282 9. The Angular Dependence of Resonance Intensities

vector case as

Iv = A[PI~I + (1 - P)I~] , (9.11a)

and for the plane case as

(9. 11 b)

where A and B are constants which describe the absolute angle-integrated

intensities. Below we shall derive expressions for the angle-dependent quantities
II [Link]' IIIpand [Link].
I v'
For the vector case shown in Fig. 9.2 the angle (j between the Ell vector and
the vector 0 along the n* or 0"* orbital can be expressed as a function of the
angle () between Ell and the surface normal n, and the polar angle IX and
azimuthal angle ¢ of the vector O. As in Fig. 9.2 we have oriented our
coordinate system with the z-axis along the surface normal and the x-axis in the
surface plane along the projection of Ell. From (9.9) we obtain the angular
dependence of the resonance intensity associated with the Ell component as

I~I = coS 2 (}COS 2 1X + sin 2 (}sin 2 IXcos 2 ¢

+ 2 sin IX cos IX sin () cos () cos ¢ . (9. 12a)

Similarly, we obtain for the angular dependence of the resonance intensity for
the perpendicular component E.L, which lies along the y-axis of our coordinate
system shown in Fig. 9.2,

(9.12b)

For the case of n* or 0"* orbitals in a plane shown in Fig. 9.3 we use similar
angular notations with y being the angle between the sample normal n and the
normal N of the n* or 0"* plane. We can express the angular term sin 2 e in (9.10)
in terms of the angles y, () and ¢ defined in Fig. 9.3 and obtain

I~ = 1 - coS 2 (}cos 2 y - sin 2 (}sin 2 ycos 2 ¢

- 2 sin y cos y sin () cos () cos ¢ (9. 13 a)

and
1* = 1 - sin 2 ysin 2 ¢ . (9.13b)

The matrix elements given by (9.12) and (9.13) when inserted in (9.11a) and
(9.11 b) yield the angular dependence of the total resonance intensity for the
"vector" and "plane" cases, respectively. Note that the resonance intensity I.L for
both the "vector" and the "plane" cases does not depend on the incidence angle ()
of the X-rays on the sample. Thus in studies where only the polar angle is
changed it simply constitutes a constant background intensity.
In practice, the orientation of a molecule on a surface is determined by
comparison of the measured angular dependence of the n* and/ or 0"* resonance
 9.4 Effect of Substrate Symmetry 283

to the one calculated according to (9. 11 a) or (9. 11 b). If P is known, these

equations contain three unknowns: for the "vector" case, A, IX and 4J, and for the
"plane" case, B, y and 4J. Hence, in each case, at least three independent
measurements as a function of polar and azimuthal angles are needed to
determine the orientation of the molecule relative to the substrate.

9.4 Effect of Substrate Symmetry

9.4.1 General Considerations

The angular dependence of the resonance intensities given by (9.12) and (9.13)
explicitly depends on the azimuthal orientation of the molecule relative to the
substrate through the angle 4J. This azimuthal dependence is eliminated in many
cases by the symmetry of the surface. The surface symmetry establishes several
equivalent in-plane chemisorption geometries which lead to the formation of
adsorbate domains. For example, the (100) surface of a face centered cubic (fcc)
substrate has fourfold rotational symmetry about the surface normal. For any
molecular chemisorption geometry on this surface another one will exist which
corresponds to a 90° rotation about the surface normal. NEXAFS spectroscopy
averages over the various geometries (domains) and this leads to simplifications
in the corresponding theoretical expressions. We note that with the possibility of
sampling increasingly smaller areas on a surface by means of X-ray and/or
photoelectron based microscopes it may be possible to obtain a spectrum from a
single domain and the above-mentioned averaging effects would be absent
(Sect. 11.1).

9.4.2 Twofold or Higher Substrate Symmetry

Equations (9.12) and (9.13) show that the azimuthal dependence of the resonance
intensities is contained in two terms which vary as cos 4J and cos 2 4J, respectively.
For twofold and higher substrate symmetry the cross-term containing cos4J is
eliminated upon averaging over domains and one obtains for the "vector" case

(9. 14a)

and

(9.14b)

It can be seen from (9.14a) that for an orbital tilt angle IX = 45° the resonance
intensity becomes independent ofthe X-ray angle of incidence (J when the orbital
direction 0 and Ell are azimuthally aligned (i.e., 4J = 0°). For the "plane" case
one obtains

(9.15a)
284 9. The Angular Dependence of Resonance Intensities

and

(9.15b)

Similar to the "vector" case the resonance intensity becomes independent of the
X-ray angle of incidence for a y = 45° tilt of the orbital plane ifthe normal of the
plane N and Ell are azimuthally aligned (i.e., ¢ = 0°).

9.4.3 Threefold or Higher Substrate Symmetry

For threefold or higher substrate symmetry the cos 2 ¢ term averages to 1/2 and
the above expressions simplify to

(9.16a)

and

(9.16b)

for the vector case and

(9.17a)

and

(9.17b)

for the plane case.

Thus for threefold or higher symmetry the azimuthal angular dependence
vanishes and the expressions are equivalent to those for cylindrical symmetry
about the surface normal. This has the important consequence that for one
specific molecular orientation the resonance intensities in both the "vector" and
"plane" cases can become independent of the X-ray incidence angle e. For
example, let us consider the case of perfect linear polarization, i.e., IE1.I = O. It is
easily seen from (9.16a) and (9.17a) that for DC or y equal to the magic angle of
54.7° the angle-dependent terms vanish. Thus for this particular orientation, i.e.,
a 54.7° tilt of the vector orbital from the surface normal or a 35.3° tilt of the
orbital plane from the surface normal, the intensity distribution measured in
NEXAFS is indistinguishable from that for a random molecular orientation.
e
Note, that for an X-ray incidence angle of = 54.7° the measured intensity
distribution is independent of the molecular orientation.
As pointed out earlier, the weak E1. component of the elliptically polarized
radiation reduces the observed resonance intensity variations as a function of
X-ray incidence in that it gives rise to a constant background, I; is largest if the
 9.5 Intensity Plots for 1t* or (1* Vector Orbitals 285

vector orbital lies in the surface plane, and it is zero if the orbital lies along the
I;
surface normal (9.16b). For the "plane" case never vanishes. Note also that for
IEl.l > 0 or P < 1 the magic angle of X-ray incidence is no longer 54.7° but is
°
given by = sin -1 Jl - Ij(3P). The magic tilt angles (X and yare still 54.7°.
It is also of interest to consider the effect of a homogeneous distribution of
molecular tilt angles around some average value, caused, for example, by
thermal motion of the molecule. This case is obtained from (9.16) and (9.17) by
integration over a range (Xl :s; (X :s; (X2 and Y1 :s; Y :s; Y2. We obtain

and

°-
Iy = HI - *<3 cos 2 I)(COS 2 Y1 + COS 2 Y2 + cos Y1 cos Y2 - 1)], (9. 19a)

I; = H3 + COS 2 Y1 + cos 2 Y2 + cos Y1 COSY2] . (9.19b)

Equations (9.18a) and (9.19a) have been derived before and can be shown to be
equivalent to [Ref. 9.8, Eq. 11].

9.S Intensity Plots for n* or (1* Vector Orbitals

The case of molecules with single n* or 11* orbitals (i.e., vectors) as shown in
Fig. 9.2 is described by (9.12, 14 and 16), depending on the symmetry of the
substrate. In the following we shall discuss two examples: (i) the azimuthal
intensity dependence of a single orbital parallel to a surface with twofold
symmetry, and (ii) the polar intensity dependence of a single orbital at a tilt angle
(X on a surface with threefold or higher symmetry.
The first case of a single orbital parallel to a surface with twofold symmetry
(9.14) is of particular importance because it can be used to accurately determine
the polarization factor P as demonstrated first for the n* resonance of formate
on Cu(110) [9.12]. We have plotted in Fig. 9.4a the 11* resonance intensity ratio
for a vector orbital parallel to the surface «(X = 90°) for normal X-ray incidence
(0 = 90°) at an arbitrary azimuthal angle </J relative to </J = 0° which corres-
ponds to the maximum intensity. It is seen from Fig. 9.4a that the azimuthal
intensity ratio is quite sensitive to the polarization factor P. If the molecular
orientation is known P can be easily determined from the intensity ratio

°
R= I(</J=90°,0) I-P
(9.20)
I(</J = 0°, = 90°) P
286 9. The Angular Dependence of Resonance Intensities

Fig.9.4. (a) Azimuthal dependence of the reson-

1.0 P= ance intensity ratio at normal incidence for a u*
--1.0 or n* orbital vector 0 parallel to the surface
.--.. 0.8 ············0.1
o ---- O.S [(9.14) with IX = (J = 90°]. Plotted is the relative
resonance intensity as the major electric field vec-
~
..... 0.6
tor component Ell is azimuthally rotated away
S:
... 0 •• from 0 by an angle r/J. For r/J = 90° the minor
~ component EL lies along 0 and causes a finite
0.2 residual intensity which strongly depends on the
polarization factor P. (b) Residual resonance in-
o tensity measured at r/J = 90° relative to r/J = 0° for
the case shown in (a) as a function of the degree of
o 20
AzImuthal Angle + .0
60 80
(Degree->
6' 1.0,...........................-4--.-.............,.
linear polarization P, Equations (9.20) and (9.21).
For P = 1, IELI = 0 and for P = 0.5, IELI = IEIII
II 0.8
~0.6
~O••
WO.2
~ 0......::.;............................................................
- 1.0 0.9 0.8 0.7 0.6 0.5
X-ray Polarization, P

and is given by

1
P=R+l· (9.21)

Note that the numerator in (9.20) is for an arbitrary (). The correlation between
P and R is plotted in Fig. 9.4b. The above method of determining P is one of the
most accurate methods known in general, with error bars of about 1% or less
[9.12, 13].
Another interesting point can be made for a vector orbital parallel to the
surface (oc = 90° in Fig. 9.2). In this case one can find an X-ray incidence angle ()
such that there is no azimuthal dependence of the measured resonance intensity,
even if the molecule is azimuthally oriented. The reason for this effect is that for a
certain choice of () the projection IEIII sin () of the dominant E vector component
in the azimuthal plane (Fig. 9.2) is identical to the minor component IE1.I. Since
the two projections are orthogonal one has an effective fourfold polarization
symmetry in the azimuthal plane and any azimuthal dependence vanishes. The
condition for this to happen can be derived from (9.14) and is given by

I-P
sin 2 () = -p-. (9.22)

For example, at P = 0.85, there is no azimuthal dependence for an X-ray

incidence angle of () = 25°.
For the second example, we discuss the polar angular dependence of the
resonance intensity given by (9.16) for threefold or higher substrate symmetry.
 9.6 Intensity Plots for n* and u* Orbitals in a Plane 287

Vector-like Orbital. Azimuthal Average. and P 0.85 =

, OO .....r-rl--,-,,.,-,..,..-,--r,-r-f"""TOl
7 6=
5°
6

5
~o ((" 0
~ ~
~ '0

r;. -.,
0 CD

5 4

.,
.0
/
.0
'"
a:: 3 a::'"
,
30°
~ ~
'iii 'iii
c c
2 .'c!!
.'!!
.=

5°
0.1l.L..L.L.W-,-'-'--'....L'--'--'-,L.'-~~
o 20 40 60 80
Polar Angle, a (Deg)

Fig.9.S. Ratio of intensities measured at normal (0 = 90°) and grazing W :s; 0 :s; 30°) X-ray
incidence and its inverse for a vector-type orbital 0 tilted by an angle C( from the surface normal. We
have assumed threefold or higher substrate symmetry (9.16) and P = 0.85

The most accurate method to determine the molecular orientation, if P is

known, is to measure the detailed (about 5 different angles) angular dependence
of the resonance intensity and then perform a least-squares fit leaving the tilt
angle as the only adjustable parameter.
Often the molecular orientation can be determined quite accurately by
measuring the resonance intensity for only two extreme sample orientations
relative to the incident X-ray beam (angle ()) and comparing the experimental
intensity ratio to that predicted by theory. The largest and most reliable
intensity ratios are obtained by comparison of spectra recorded at grazing
(() ~ 30°) and normal (() = 90°) X-ray incidence angles. We have therefore
plotted in Fig. 9.5 the intensity ratio /(90°)//(()) and its inverse for 5° ~ () ~ 30°
as a function of the tilt angle Q( of the n* or (7* orbital from the surface normal,
assuming P = 0.85. For clarity we have plotted the intensity ratio on a linear or
on a logarithmic scale, as appropriate. The plots in Fig. 9.5 are especially useful
for obtaining a quick estimate of the molecular orientation.

9.6 Intensity Plots for 7[* and (1* Orbitals in a Plane

Figure 9.3 illustrates the parameters employed when the n* or (7* orbitals span a
plane. The relevant equations for various substrate symmetries are given by
(9.13, 15 and 17). Let us consider the same two examples as discussed above for
the case of a vector orbital.
288 9. The Angular Dependence of Resonance Intensities

Plane-like Orbital. Azimuthal Average. and P =0.85

7 e= 2.0
5°

°
~
a

a ~
=
5'" .....
..,
.0
to
..,
.0
to
a:: a::
~ ~
·iii ·iii
c: c:
~
2 ~
E E

5°
o 5°
O~~~~~~LU~
020406080 o 20 40 60 80
Polar Angle, y (Deg) Polar Angle, y (Deg)

Fig.9.6. Ratio of intensities measured at normal (9 = 90°) and grazing (5° ~ 9 ~ 30°) X-ray
incidence and its inverse for a plane-type orbital tilted by an angle y from the surface. We have
assumed threefold or higher substrate symmetry (9.17) and P = 0.85

For a twofold symmetric substrate the resonance intensity will exhibit a

strong azimuthal dependence if the plane containing the orbitals is perpendicular
to the surface (e.g., a standing-up benzene molecule). At normal X-ray incidence
(0 = 90°) the azimuthal intensity dependence for this case, characterized by
y = 90° (Fig. 9.3), is also given by the plot in Fig. 9.4a, if we take ¢ to be the angle
between Ell and the orbital plane [note that this definition of ¢ differs by 90°
from that used in (9.15) and Fig. 9.3].
The case of threefold or higher azimuthal symmetry for an orbital plane is
considered in Fig. 9.6. Here the intensity ratio /(90°)//(0) and its inverse are
plotted for 5° ~ 0 ~ 30° as a function of the tilt angle y of the normal N of the
molecular plane relative to the surface normal n. As for the corresponding case
of vector-type orbitals, (Fig. 9.5) we have assumed P = 0.85. This plot is useful
for a quick estimate of the polar tilt angle of the plane in an aromatic ring or the
1t plane of a triple bond.

9.7 An Example: The 1l* Resonance Intensity in Graphite

A nice example of a strong angular dependence of a resonance and a test case for
our theory is provided by the angle-dependent NEXAFS spectra of highly
oriented pyrolytic graphite [9.14] shown in Fig. 9.7a. The six-membered rings of
carbon atoms all lie in parallel planes, parallel to the surface of the crystal and
 9.7 An Example: The 11:* Resonance Intensity in Graphite 289

perpendicular to the crystallographic c-axis, as indicated in Fig. 9.7a. As in the

benzene molecule shown in Fig. 9.1, the n* orbitals can be described as vectors
perpendicular to the basal plane, i.e., along the c-axis. The NEXAFS spectra
exhibit a sharp resonance near 285 eV, which corresponds to a transition to the
first empty n* state. This resonance is strong at grazing X-ray incidence, when
the electric field vector E has a large projection along the direction of the n*
orbital, and it vanishes at normal X-ray incidence, when E is perpendicular to
the n* orbital (also see Fig. 6.30). The experimental geometry for the spectra in
Fig. 9.7a was such that the minor electric field vector component E1. was always
in the surface plane such that the intensity change was solely due to the different
projection Ell cos eof the major component in the direction of the n* orbital, as
shown in Fig. 9.7a. This case is therefore described by the geometry shown in
Fig. 9.2 with ex = 0 and according to (9.11a) and (9.16) the angular dependence of
the peak intensity should go as Iv ex. cos 2 e. Note that the angular dependence
can also be understood simply from (9.9) with t5 = e. The theoretical expectation
is confirmed by the plot of the measured n* intensity versus cos 2 e shown in
Fig.9.7b.

Highly Oriented Pyrolytlc Graphite

(a) A e~EII
~
I

8=
~/
30°

0 40° 0
50°
0 0
"0
Qj
:; 0 0
c
e
u 0 0
'"
u:i
iii 0 0
'0
I-
0 0

0 0 Fig.9.7. (a) NEXAFS spectra of highly oriented pyrol-

ytic graphite (monochromator graphite) as a function
275 285 295 305 315 325 335 345
of angle of X-ray incidence [9.14]. The basal plane of
Photon Energy (eV)
graphite, consisting of sheets of six-membered rings of
18 carbon atoms (Fig. 6.30), is parallel to the surface, and
~ 16 (b)
'(ij
c 14 perpendicular to the crystallographic c-axis. The 11:*
'"
C 10
12 orbitals lie along the c-axis and peak A corresponds to
a transition to the lowest empty 11:* states. The sample
« 86
-"
orientation in the X-ray beam was such that E1. was
4
''""
0.. 2 always in the surface plane and Ell was at an angle (J to
0 the c-axis, as shown. (b) Plot of peak A intensity as a
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
function of cos 2 (J which confirms the expected angular
cos 28 dependence of the 11:* resonance
290 9. The Angular Dependence of Resonance Intensities

9.8 Angular Dependence of Intensities in Difference Spectra

As pointed out in Sect. 7.1.2, difference spectra often provide a valuable tool for
identifying angle-dependent features. Therefore we need to briefly discuss what
can be quantitatively learned from analysis of the intensities of such spectra. Let
us therefore look at the mathematical expressions for the intensity of difference
spectra for the two important cases of vector and plane orbitals without
preferred azimuthal orientation, as discussed in Sect. 9.4.3.
For a vector orbital the total resonance intensity is given by (9. 11 a), and the
azimuthally averaged intensities of the two E vector components are given by
(9.16). Rewriting, the total intensity can be expressed as

(9.23)

Upon subtracting two spectra recorded at different X-ray incidence angles () and
(}1for the same sample (and hence the same orbital tilt angle oc), the last term in
(9.23) drops out to yield

(9.24)

where C is a normalization constant, and we have defined a geometry factor

g.(oc) = 1 - (3/2) sin 2 oc.
Similarly, for a plane orbital we can rewrite the azimuthally averaged total
resonance intensity given by (9.l1b) and (9.17) as

(9.25)

Upon subtraction of two spectra recorded at X-ray incidence angles () and (}1 for
the same orbital tilt angle y we obtain
(9.26)

where the geometry factor is given by gp(Y) = 1 - 3 cos 2 y.

Unfortunately, examination of (9.24) and (9.26) reveals that the angles oc and
y, which determine the molecular orientation, cannot be determined from the
difference spectra alone. This problem arises from the fact that both the constant
C and oc or yare unknown in (9.24) and (9.26). Hence a fit of difference intensities
as a function of () according to (9.24) and (9.26) always has the general cos 2 (}
dependence and only determines the product Cg.(oc) or Cgp(Y) as a scale factor.
Note, that this is different if the peak intensities of the original spectra are fitted.
In this case (9.23) or (9.25) are used and, if P is known, resonance intensities
obtained from curve fits of two or more spectra recorded at different angles ()
uniquely determine A and oc or Band y.
The ambiguity encountered in the analysis of difference spectra can be
circumvented by use of a "standard". By employing the same experimental
 9.8 Angular Dependence of Intensities in Difference Spectra 291

arrangement for the "standard" and the unknown system one can eliminate all
experimental artifacts by normalization to the edge jump. Then the normaliz-
ation constant C in (9.24) or (9.26) can be assumed to be the same in both cases.
For example, let us assume that the orientation of CO on Ni(lOO) and therefore
the geometry factor gv(cxNJ is known. One can then determine the constant C
simply from the scale factor Cgv(cx Ni ), which is obtained from a fit of the
difference intensities for the 0"* resonance for this system according to (9.24) (or
similarly for a plane-like orbital). Therefore the scale factor Cg.(cx x ) derived for
the sample in question, CO on surface X, can be used to extract the tilt angle CX x
for this system. We shall use this procedure in Sect. 10.7 for the determination of
the hydrocarbon chain orientation in Langmuir-Blodgett films.
Finally, we note that the use of a "standard" can also eliminate the necessity
of knowing the polarization factor. In this case it is necessary to compare the
intensities determined from curve fits of the original spectra. This method was in
fact used in the very first NEXAFS study by Stohr et al. [9.15] where the
orientation of NO on Ni(l00) was determined by using CO on Ni(l00) as a
"standard".
10. Selected Applications of NEXAFS

Here we discuss selected examples of how NEXAFS has been used to obtain
information on the electronic and crystallographic structure of molecular
adsorption systems. Our examples cover a wide range of molecular adsorption
energies, from weak van-der-Waals like interactions to strong chemical bonds,
and address a diversity of molecules, ranging from diatomics to larger rings and
chains.

10.1 What Can We Hope to Learn?

It has been shown in Chap. 6 that NEXAFS spectroscopy is sensitive to changes

in the electronic and geometric intra-molecular structure. In addition, it reveals
the molecular orientation on the surface. All this information is largely con-
tained in the position, width and intensity of the n* and a* resonances. In this
chapter we wish to relate the information obtained from analysis of the
resonances to fundamental concepts underlying our understanding of the sur-
face chemical bond. We shall emphasize chemisorption, i.e., bonding to the
surface through molecular orbitals, although examples of van-der-Waals bon-
ding, often referred to as physisorption, will also be given.
In molecular adsorption systems there may be several extra-molecular
bonding interactions, the most important one typically being the bond with the
underlying substrate. Lateral interactions between the molecules may also play
an important role, or for complex molecules there may be bonding through
more than one functional group. Furthermore, molecular fragmentation may
result in the formation of surface species quite different from the original gas
phase molecules. The question is how these various interactions manifest
themselves in a NEXAFS spectrum, or conversely, what we can learn about the
interactions from analysis of the spectrum. Before we discuss specific case studies
let us briefly review some general concepts underlying molecule-surface inter-
actions.
Because of the close relationship between molecular chemisorption on
metals and organo-transition-metal chemistry it is instructive to first consider
general bonding concepts in organometallics [10.1,2]. We have already encoun-
tered the two most fundamental molecule-metal bonding schemes in Sect. 6.1.1
in conjunction with the molecules CO and C 2 H 4 , namely donor versus acceptor
 10.1 What Can We Hope to Learn? 293

bonds. In unsaturated molecules, i.e., those with n as well as rr intra-molecular

bonding, both donor and acceptor contributions to the chemisorption bond are
typically present. The donor contribution involves a filled bonding MO (typic-
ally the HOMO) and electron transfer from the molecule to the metal. The
acceptor bond is formed by an empty anti bonding MO, usually of n symmetry,
with electron transfer from the metal to the molecule. Other types of
molecule-metal bonds involve a lone pair MO on the molecule, e.g., in NH 3 ,
H 2 0, or in alcohols, with electron transfer from the molecule to the metal (Lewis
base donors). In dissociated molecules, broken or "dangling" bonds may exist
and the molecule may affix itself to the surface by "healing" the broken bond.
There are two prototypes of donor and acceptor bonds in unsaturated
systems. In carbonyls the rr-donor and n*-acceptor contributions are syn-
ergically related, with the latter making a larger net contribution. Olefins, on the
other hand, are either predominantly n-donors or n*-acceptors, depending on
the metal [10.1]. It should be noted that although olefin donor bonds involve
the filled n orbital, they are often referred to as rr-donors, where the symmetry
label refers to the rr-like symmetry of the filled n system relative to the
molecule-metal bond axis, as schematically shown in Fig. 10.1. In analogy to
organometallics, unsaturated linear hydrocarbons are expected to n-bond to the
surface in a lying-down geometry. Those with donor bonds should exhibit a
largely unperturbed C=C bond length and the rr-like bonding symmetry with
respect to the surface normal is expected to favor random azimuthal orientation.
In contrast, n*-acceptor systems may exhibit substantial lengthening of the
C=C double bond, all the way to the single bond length value, owing to the
anti bonding nature of the n* system. Also, the n-like symmetry of the n* system
with respect to the surface normal (compare Fig. 10.1) is expected to lead to
preferential azimuthal bonding~
The predictions by organo-transition-metal chemistry are indeed borne out
by experimental results for chemisorbed ethylene. As discussed previously in

(a) " u "-Donor Bonds

1~ Bo nd Axis & ~1
~ Sur1ace Normal :
(b ) 7T*-Acceptor Bonds

~ H~.~b,q(ql
t
5.

H? "Q H

Fig. 10.1. Schematic representation of (a) donor and (b) acceptor bonds in molecular chemisorption,
using the molecules CO and C zH 4 as examples. In donor bonds electrons are transferred from the
molecule to the surface and vice versa for acceptor bonds. Note that in ethylene the donor bond
involves the filled 1t orbitals, yet it is often referred to as a a-donor bond owing to the a-like
symmetry of the 1t orbitals relative to the surface normal
294 10. Selected Applications of NEXAFS

Sect. 8.6.3 and shown in Fig. 8.22, C 2 H 4 is found to bond with the C-C axis
parallel to the surface on all metals studied, as expected. The C-C bond
lengthening observed with increasing interaction with the surface is accom-
panied by a reduction and broadening of the n* resonance intensity. This is a
direct manifestation of the transition from a donor-type bond on Ag to a n*-
acceptor bond on Pt(111). As discussed in Sect. 6.1.1 for CO, the n* resonance
intensity is expected to decrease with increasing strength of the n*-acceptor
bond (back bonding) and the resonance width to increase with increasing mixing
of metal dn and pn orbitals with the molecular n* orbital. This is observed in
Fig. 8.22b on going from the gas phase spectrum at the bottom to the
C 2 H 2 /Pt(111) spectrum at the top. Also, for ethylene on the twofold symmetric
Ag(110) surface no azimuthal ordering is observed [10.3], in agreement with a (J-
donor interaction. Unfortunately, no spectra have been measured for the
twofold symmetric Pt(llO) surface, but here azimuthal ordering is expected
owing to the n*-acceptor nature of the bond.
This quick review of the ethylene results only serves as an introductory
example of how the nature of the molecule-surface bond can be deduced from
the NEXAFS spectra. We shall come back to the interesting example of C 2 H 2
on Pt(111) in Sect. 10.4.2. More detailed and instructive examples of the effect of
backbonding in diatomic adsorbates will also be discussed below for CO, O 2
and C 2 on metal surfaces.
While studies of small molecules are particularly suited for detailed studies of
the most elementary bonding interactions, larger molecules lend themselves to
the investigation of multifunctional chemisorption bonds and/or lateral inter-
action effects. Here interactions of different functional subgroups should be
revealed in the spectra by the differential change of specific, subgroup-related
resonances, e.g., the intensity reduction of a C=O n* resonance, relative to a
C=C n* resonance. Also, multifunctional bonding will in general lead to specific
polar and azimuthal molecular orientations on the surface. Similarly, lateral
interactions are expected to affect the molecular orientation. For example, the
ring-like benzene molecule may be expected to lie down on the surface in a n-
bonding configuration at low coverage while at higher coverage lateral inter-
action ("crowding") may force the rings to stand up. Such effects should be easily
revealed by NEXAFS and below we shall give examples of such effects for ring-
and chain-like molecules.
Finally, one of the most fundamental surface science problems, that of
molecular dissociation, can in many cases be addressed by NEXAFS. Since the
NEXAFS resonances are associated with intra-molecular bonds, the dis-
appearance of resonances may in some cases be associated with bond breaking.
We shall discuss below a particularly beautiful example, that of thiophene on
Pt(111), where the disappearance of the C-S resonance signifies desulfurization
of the ring. Another more complicated example, the dissociation of benzene on
Mo(llO), will also be presented. In this case, the fragments of the molecule,
benzyne and atomic C, can be uniquely identified.
 10.2 CO on Pt(111) and the Effects ofNa and H2 295

The case studies below are organized in order of increasing molecular size
and/or by grouping molecules according to shape. We shall start with di-
atomics, then discuss ring-like and finally chain-like molecules.

10.2 CO on Pt(1l1) and the Effects of Na and H2

Carbon monoxide is the most widely studied molecule in surface science. The
main reasons for this popularity are its simple diatomic nature and its import-
ance in the famous Fischer-Tropsch synthesis of hydrocarbons and alcohols
from CO and H2 [10.4]. The generation of CO plus H 2, so-called synthesis gas,
from coal is the first step in the production of bulk chemicals and liquid
hydrocarbon fuels [10.5]. The rise and fall of the commercialization of the
Fischer-Tropsch process has been tied to the availability of cheap petroleum or
to political considerations, such as in war-time Germany or, more recently, in
South Africa.
The catalytic hydrogenation of CO is enhanced by so-called promoters, in
particular, alkali metals. The original Fischer-Tropsch catalyst, for example,
contained both iron and cobalt, with added K2 C0 3 and copper as promoters.
Since Fischer and Tropsch's work around 1925 the promotion or, conversely,
the poisoning of the CO hydrogenation process has not only been the subject of
substantial, largely empirical efforts to improve catalysts [10.5] but it has also
stimulated a great number of experimental and theoretical investigations of
model systems [10.6]. One important issue involves understanding how alkali
metals induce electronic modifications in the bonding of CO to the metal
substrate and thereby perturb its geometric and electronic structure in the
chemisorbed state. We shall start with an example of a NEXAFS study of this
problem. The second example will deal with the chemisorption of CO on Pt(l11)
in the presence of hydrogen gas, obviously another important aspect of the
Fischer-Tropsch reaction. This latter example also demonstrates the special
capability of fluorescence yield NEXAFS of investigating surfaces under "reac-
tion conditions" [10.7] similar to those in real catalytic reactions.

10.2.1 CO/Pt(I11) and CO/Na/Pt(I11)

On clean metal surfaces CO typically chemisorbs in an upright geometry via the
C 5(1 lone pair donor bond with stabilization through backbonding of metal
orbitals with the 2n* antibonding orbitals of the molecule (Fig. 10.2a). Alkali-
metal promoters are believed to enhance the CO hydrogenation by weakening
the C-O bond and strengthening the carbon-metal bond. In the Blyholder
model [10.8] the C-O bond is weakened in the presence of electron-donating
alkali-metal absorbates by an increased back donation of electrons into the 2n*
orbital, as schematically shown in Fig. 10.2b. Because the 2n* orbital is anti-
296 10. Selected Applications of NEXAFS

(0)

5a ---==~1

Pt(111)
Fig. 10.2. (a) Local molecular orbital bonding picture of CO in an atop site of a Pt surface in the
Blyholder model [10.8]. The bonding consists of charge donation from the molecular 50" orbital to
the metal and charge back donation from the metal d-orbitals into the 2n* MO. (b) In the presence
of co-adsorbed Na the back donation of charge from the metal to the 2n* MO is enhanced by a
Na-Pt(llI) donor bond, as shown

bonding, a diminished C-O bond strength is expected . . There has also been
speculation that on the alkali-metal-promoted surface CO may be bonded as a
tilted or side-on bonded species. Such a geometry may be expected to lead to
even larger metal-2n* interaction and may serve as a precursor for CO
dissociation [10.6]. It is apparent that NEXAFS is a well suited technique for
exploring the orientation of CO on the surface and the metal-2n* interaction,
owing to the fact that the 2n* orbital gives rise to the pronounced n* resonance
of CO.
Figure 10.3 shows the normal incidence NEXAFS spectra obtained by Sette
et al. [10.9] at the C K-edge for CO on clean Pt(111) and for CO on Pt(111) that
was precovered with 0.2 monolayer ofNa metal. Both spectra are dominated by
a strong n* resonance near 288 e V (20' -+ 2n* excitation). The absence of the 0'*
resonance at normal X-ray incidence directly reveals that for both cases shown
in Fig. 10.3 CO stands up on the surface. The major changes in the n* resonance
for the CO / Na/ Pt(lll) system relative to CO / Pt(l11) are an increased full
width at half maximum from 1.7 to 2.5 eV, a 30% decrease in intensity, and a
0.6 eV shift to lower photon energy. The decreased intensity of the n* resonance
with respect to the underlying atomic-like K-edge absorption step is directly
evident from the spectra in Fig. 10.3c which were obtained from the original
data by subtraction of a background shown dashed in Fig. 10.3a and b. The shift
of the n* resonance follows that of the C Is binding energy as proven by XPS
measurements on the same surface [10.9]. The broadening and intensity reduc-
tion is more complex and will be discussed later.
NEXAFS spectra recorded for the same two surfaces at 20° grazing X-ray
incidence (E close to surface normal) are shown in Fig. 10.4 for both the C and 0
K-edges. Analysis of the angular dependence of the n* intensity yields an
orientation of the CO axis within ± 15° of the surface normal for CO / Pt(111)
and a tilt angle of 10° ± 15° with respect to the surface normal for
 10.2 CO on Pt (111) and the Effects of Na and H2 297

1Tol
, Fig. 10.3. NEXAFS spectra re-
(c) :: corded at normal X-ray incidence
1.3 (a) II
jI above the C K-edge of CO chemis-
I'
I orbed (a) on clean Pt(l1l) and (b)
on Pt(I11) with a preadsorbed 0.2
1.2
monolayer of Na [10.9]. XPS den-
E otes the Cis binding energies rela-
(;
"0
Q; tive to the Fermi level measured by
>= 1.1 z,-=-,..,,-L-L-L,-L--L-L-L.....J.--1
280 300 320 photoemission [286.5 eV for
"
~ CO/Pt(111) CO/Pt(l1l) and 286.1 eV for
o CO/Na/Pt(1 I 1)]. The dashed cur-
~
UJ ------------ ves are functions used to subtract
o
1: the background with parameters

~I
o determined by a best fit in the pre-
c..
0.55 edge region. The resulting spectra,
f normalized to the edge jump, are
shown III (c) as dashed
[CO/Pt(I11)] and solid
[CO/Na/Pt(I11)] lines. The da-
0.50
--- --- ---- shed curve has also been shifted by
0.6eV to lower energy to align the
280 290 300 310 320 n * resonances
Photon Energy (eY)

"0
Q;
>=
"e
"t
~
UJ

0 (b) 11T·
t 1.1
0
c..
Fig. 10.4. Grazing (20°) X-ray incidence
1.0 NEXAFS spectra recorded above the (a)
carbon and (b) oxygen K-edges for the
1.1 same two surfaces as in Fig. 10.3 [10.9].
Note the reduction in the n* and the shift
of the (J * resonances in the spectra re-
1.0 corded for the case of coadsorbed Na. The
XPS binding energies are also indicated.
0.9 The C Is binding energies are reported in
the caption of Fig. 10.3, and the 0 Is val-
530 540 550 560 ues are 532.0eV for CO/Pt(lll) and
Photon Energy (eY) 531.3eV for CO/Na/Pt(lll) [10.9]
298 10. Selected Applications of NEXAFS

CO/Na/Pt(111). However, within our experimental uncertainty we cannot

unequivocally distinguish between the two cases.
More than 20% of the decreased intensity of the n* excitation for the
CO /Na/Pt(111) surface revealed by Fig. lO.3c remains unexplained even if we
assume a 10° molecular tilt. The decrease of the n* resonance intensity can be
attributed to filling of the 2n* level caused by enhanced back bonding. This leads
to fewer unoccupied 2n* states, and the intensity of the 2a -+ 2n* transition is
reduced. This effect has also been observed by Riihl and Hitchcock in a
systematic study of transition metal carbonyls [10.10]. Also, the increased metal
character of the totaln* state in the presence ofNa leads to a reduced lifetime of
the final state of the 2a -+ 2n* transition because of delocalization and this
causes the observed broadening for CO/Na/Pt(111), evident from Fig. 10.3c.
We cannot exclude a small inhomogeneous broadening contribution to the
width of the n* resonance for CO/Na/Pt(111) caused by different CO environ-
ments. However, high-resolution electron-energy-Ioss spectroscopy spectra for
this surface clearly show that one CO species (1690 cm -1) dominates.
The observed movement of the a* resonance towards lower energy in the
presence of Na is direct experimental evidence for an increased c-o bond
length. How can we quantitatively estimate this bond lengthening? From the
width of the n* resonance it is clear that CO is strongly chemisorbed on the
surface in both cases. We also expect some bonding shift upon chemisorption,
possibly even a differential shift of the C and 0 Is IPs. Furthermore, the
situation is complicated by the fact that for carbon-oxygen bonds in the gas
phase a change in hybridization leads to different absolute energy shifts at the C
and 0 K -edges, both of the IP and of the a* resonance positions, as shown in
Fig. 8.8. Thus we have the complicated situation discussed in Sect. 8.6.4, and, as
suggested there, we need to consider other information in order to determine the
bond length.
This information is supplied by the measured XPS binding energy shifts
between CO/Pt(111) and CO/Na/Pt(I11). The measured values relative to the
Fermi level are 286.5 eV (C Is) and 532.0eV (0 Is) for CO/Pt(111) and 286.1 eV
(C Is) and 531.3eV (0 Is) for CO/Na/Pt(I11) [10.9]. Thus the binding energy
of both the C and 0 Is levels is lowered by about the same amount, ~ 0.5 eV.
Furthermore, as mentioned earlier, the n* position follows this trend (Fig. 10.4).
We attribute this to a bonding shift which we need to consider in the determina-
tion of the relative shift of the a* resonance. By referencing the a-resonance
positions in Fig. 10.4 to the Fermi level (marked XPS) we obtain a change in Aa
of - 4.0 ± 0.5 eV for both the C and 0 K -edge spectra.
We now use the variation of the relative resonance position Aa with bond
length R, which according to Fig. 8.8b is approximately linear for C-O bonds
with a slope of [see (8.2)] a = 29 ± 3 eV/ A. The - 4.0 ± 0.5 eV shift then yields
AR = + 0.14 + 0.03 A. Additional, unpublished NEXAFS spectra reveal that
the change in A a , and therefore AR, decreases with decreasing Na coverage. If we
assume that the C-O distance of CO on clean Pt(lll) is 1.13 ± 0.03 A, as judged
by the bond lengths in a variety of carbonyls [10.11], then the C-O distance for
CO coadsorbed with Na is 1.27 ± 0.06 A.
 10.2 CO on Pt (111) and the Effects of Na and H2 299

Because of expected similarities between the electronic structures of small

molecules chemisorbed on metal surfaces and those coordinated to monomeric
and polynuclear metal compounds, it is interesting to make such a comparison
for co. There are no precedents for CO bonds as long as 1.27 A in molecular
carbonyls when CO bonds only via its C atom [10.1, 11]. In such compounds,
the analogs of upright CO orientations on the surface, the CO distance typically
spans the range 1.12 to 1.22 A and the vibrational frequencies range from 2100
to 1600cm- 1 [10.1]. The low end of this frequency range is traditionally
associated with carbonyls in bonding environments that enhance donation to
the CO 2n* level. This occurs in clusters (and on surfaces) as the ligand passes
from terminal to bridging (two metal) and triply bridging (three metal) geo-
metries. Comparable red shifts also develop in monomeric carbonyls as COs are
replaced with a-donor amine ligands possessing no low-lying n*-acceptor
orbitals [10.1].
Since chemisorbed CO on Na-precovered Pt(111) is within 15° of normal to
the surface plane, it is unlikely that the long CO distance results from direct
interactions of alkali-metal adatoms with the 0 end of CO. Na preadsorption
also significantly reduces the CO n* resonance intensity. This suggests that
enhanced electron donation to its 2n* levels plays a key role in attenuating the
CO bond order. In the extended Blyholder model shown in Fig. 10.2, supported
by the present NEXAFS work, the alkali metal would increase availability of
surface electrons for back donation. Alkali-metal atoms might also force ad-
sorbed COs into threefold sites. Since the bond lengthening suggested by
NEXAFS for the CO /Na/Pt(111) system is beyond the realm attributed to n*
filling in structurally characterized compounds and exceeds the nominal C=O
double bond length of 1.21 A (e.g., in H 2 CO), Sette et al. [10.9] suggested that
the increased CO distance also reflects rehybridization of Sa, 1n, and 2n*
orbitals.
The determination of the intramolecular structure and molecular orienta-
tion for the CO/Na/Pt(111) system by NEXAFS is only one of many investiga-
tions of CO chemisorption on metal surfaces, as is evident from Appendix B. Its
appeal lies in the ease with which important and unambiguous information is
directly revealed by the NEXAFS spectra, without the need for an extended data
analysis.

10.2.2 CO/Pt(lll) in the Presence of H2 Gas

In Chap. 5 we discussed the use of fluorescence detection for NEXAFS spectro-
scopy. In particular, Fig. 5.18 shows a system designed for studies where the
sample can be kept in a gas, close to atmospheric pressure. This system was
employed by Parker et al. [10.12] in their study of the CO /Pt(111) system in the
presence of hydrogen gas at different partial pressures. The goal of the study was
to investigate the differences in CO adsorption caused by the presence of
hydrogen gas relative to that on the clean surface.
In their experiment, the clean Pt(l11) crystal was given a saturation expos-
ure of CO at 100 K in a sample preparation chamber and was then raised into
300 10. Selected Applications of NEXAFS

the reaction chamber as shown in Fig. 5.18. NEXAFS spectra were recorded at
normal X-ray incidence to optimize the prominent n* resonance intensity as
shown in Fig. 10.3. The monochromator was positioned at an energy corres-
ponding to the center of the n* resonance and the carbon Ka. fluorescence yield
intensity was measured as a function of time while the temperature of the Pt
crystal was ramped at a rate of 1 K/s. Since the so-measured n* resonance
intensity is linearly dependent on surface coverage, the concentration of ad-
sorbed CO could be determined as a function of temperature. The experiment
was performed in vacuum and at several different partial pressures of hydrogen.
The fluorescence intensity could be converted into absolute coverage e since the
saturation coverage at 100 K had previously been established to be 9.6 x 10 14
molecules/cm 2 , corresponding to e = 0.64 monolayers. At the highest temper-
atures (T > 500 K) CO was known to have desorbed, and the residual detector
signal at these temperatures therefore corresponded to e = o.
The results of measurements in vacuum and in 0.01 Torr hydrogen are
shown in Fig. 10.5. The vacuum experiment shows a drop in CO coverage
beginning at 340 K, falling to zero by 470 K. This corresponds to the thermal
desorption of CO from clean Pt(l11) with the maximum desorption rate
occurring at the point of inflection, 399 K. In the presence of 0.01 Torr hydrogen,
the CO concentration shows a first decrease between 130 K and 190 K, with an
inflection point at 168 K. This decrease indicates the loss of about one fourth of
the original CO adlayer, from e = 0.64 to e = 0.5. The CO coverage remains at
this latter value until about 300 K when it starts falling to zero, with an inflection
point at 386 K, 13 K lower than for the vacuum desorption case.

Displacement of CO on Pt(111) by Hydrogen

til • Vacuum
Q; 0.8
>-
os o 0.01 Torr Hydrogen
"0
g 0.6
::2
Q) 0.4
Cl
os
Q;
1) 0.2
()

8 0.0

o 100 300 500 700

Temperature (K)

Fig. 10.5. CO coverage on Pt(ll1) derived from the fluorescence yield intensity of the 7t* resonance
in a normal X-ray incidence NEXAFS spectrum as a function of temperature [10.12]. The curve
connecting squares was obtained when the crystal was heated in vacuum, the curve connecting
circles corresponds to heating the crystal in the presence of 0.01 Torr hydrogen gas. In this latter case
the reduction in coverage around 170 K is due to replacement of about 25% of the CO molecules by
hydrogen
 10.3 Molecular Oxygen on Pt(lll) and Ag(llO) 301

The results in Fig. 10.5 show convincingly that the interaction of CO with
the Pt(111) surface is significantly influenced by the presence of hydrogen gas.
Parker et al. attribute the initial reduction in CO coverage near 170 K in the
presence of hydrogen to a displacement reaction, where CO molecules in the
compressed layer (0.5 < e < 0.64) are replaced by hydrogens. At first sight such
a displacement process appears unlikely since on Pt(111) the heat of adsorption,
in the limit of zero coverage, for CO (31 kcal/mole) is larger than that of
hydrogen (19 kcal/mole). This unfavorable ratio, however, does not apply to the
high coverage limit where repulsive interactions in the adsorbed layer, mostly
between COs, can reduce the desorption energy of CO to a value smaller than
the heat of adsorption for hydrogen. Hence the adsorption of hydrogen is
energetically favored over that of CO and the latter is replaced until the lateral
interaction between COs has decreased to a level where CO adsorption is
favored over hydrogen adsorption. Similarly, the shift of the inflection point of
the main desorption channel at higher temperature in the presence of hydrogen
can be attributed to a slight reduction (~1 kcal/mole) in the activation energy
for desorption. This may occur by adsorbed hydrogen forcing COs from atop
into less strongly bound bridge sites or simply by direct CO-H interactions.
Similar results have also been observed for the CO/Ni(100) system [10.13],
and this may indicate that displacement of a compressed CO adlayer by
hydrogen on transition metal surfaces is a quite general phenomenon. The
above studies point out the importance of surface chemistry investigations at
high pressure. Since real catalytic processes always occur in a gaseous or liquid
environment, it is apparent that every effort should be made in model ex-
periments to approximate such conditions as closely as possible. The above
experiments are a first step in this direction.

10.3 Molecular Oxygen on Pt(I11) and Ag(llO)

The interaction of oxygen with metal surfaces is an ever-present phenomenon in

our world and hence it is important to understand it. At room temperature, the
interaction typically leads to dissociation of the molecule and to the formation
of strong bonds of the oxygen atoms with the metallic surface. This oxidation
reaction may lead to the formation of a protective oxide overcoat as for
aluminum metal. At lower temperature, the molecules impinging on the surface
may remain intact and exist in chemically different states which can be regarded
as precursors to dissociation. At the lowest temperatures one may envisage a
weakly van-der-Waals bonded "physisorbed" state and at higher temperatures a
chemically bonded "chemisorbed" state. This simple picture has indeed been
verified by experiment for several systems [10.14-16]. The purpose of the
following sections is to show that the different molecular states can be well
characterized by NEXAFS. Information is obtained on the geometric, electronic
and magnetic structure of the O 2 molecule in different phases. We shall show
302 10. Selected Applications of NEXAFS

that O 2 can exist in a physisorbed state, a chemisorbed superoxide O 2 and a

peroxide O~ - state. These states can be regarded as progressive steps toward
dissociation and therefore as precursors for the oxidation reaction.

10.3.1 Physisorbed Versus Chemisorbed O 2 on Pt(111)

Despite the proven existence of physisorbed (van-der-Waals bonded) and
chemisorbed (chemically bonded) molecular precursors to dissociation men-
tioned above [10.14-17] there are many unanswered questions regarding the
electronic, geometric and magnetic structure of molecules in such states. The
present section deals with the characterization of the 02/Pt(111) system [10.18],
which exhibits two well-defined sequential molecular precursors [10.16, 19].
As shown by the potential energy diagram in Fig. 10.6, the reaction of
molecular oxygen with the Pt(lll) surface proceeds in three steps: physisorption
[10.16], chemisorption [10.20], and dissociation [10.21]. In practice, the
barriers between the three potential wells, separating the three forms of oxygen,
can be overcome by thermal excitation. Under controlled experimental condi-
tions the physisorbed state (T < 30 K) can be converted by heating into the
chemisorbed state, allowing a direct characterization and comparison of the two
states. Above 150 K the chemisorbed molecular state converts into the disso-
ciated atomic state [10.21].

.
>-
~
I:
W
'0
.
:;::
I:

(; Reaction
Q. Coordinate
Fig. 10.6. Schematic potential energy diagram
versus reaction coordinate for the interaction of
O 2 with the Pt(ll1) surface. At low temper-
Physisorbed 02
El =2.8 kcal/mole atures (T < 30 K) the molecule is trapped into a
physisorbed state with binding energy E 1
= 2.8 kcal/mole [10.16] and may be thermally
activated (T > 35 K) to a chemisorbed state
with E2 = 8.8 kcal/mole [10.20]. Above 150 K

~
Chemisorbed atomic 0
the chemisorbed molecular state dissociates into
an atomic state with a binding energy of about
EJ '" 55 kcal/mole E3 = 55 kcal/mole [10.21]

Figure 10.7 shows a comparison of the polarization dependent NEXAFS

spectra for a thin multilayer (~9 layers) and monolayers of physisorbed and
chemisorbed O 2, taken at normal and at 7° glancing X-ray incidence, respect-
ively. Oxygen multilayers and the physisorbed molecular state were prepared by
controlled O 2 exposures of the clean Pt(l11) crystal at 17 K. The chemisorbed
state was prepared either by heating the physisorbed layer to 80 K or by dosing
the Pt(l11) crystal at 80K. Both-procedures led to nearly identical spectra. All
 10.3 Molecular Oxygen on Pt(1l1) and Ag(llO) 303

(e)
Multilayer ~/Pt(111)

E±
10
(a) (b)
t
~

....en
·2
=' 1.2
(d) (e)
...
..c:i
1.0 (I)
~
-c 0.8 Physisorbed ~/Pt(111)
Ol
>=

~
0.6
=
.......
0 0.4

~'"'"' 0.2

OJ
...
:;:J 0.6 (g) (h)
(i)
""''" 0.5
Chemisorbed 02/Pt(111)
,,0

AA
0.4
"1 •
0.3

0.2

0.1

550 530 540 550

Photon Energy (eV)

Fig. to.7a-i. Partial electron yield NEXAFS spectra of O 2 in different phases on Pt(lll), curve fits
and structural models. The spectra in the left column were recorded at normal X-ray incidence, those
in the center at grazing (70) incidence. All spectra were recorded at 17 K and are normalized to the
incident flux and background. Spectra (a) and (b) are for a 9 layer O 2 film, condensed at 17 K. The
structural model for this film shown in (c) consists of O 2 molecules lying down in the first layer and
tilted molecules (0-0 axis 3SO from surface normal) in the layers further away from the surface. In (c)
we have assumed Pt atoms (large filled circles) with a diameter given by the nearest neighbor
distance in Pt metal (2.774 A) and have approximated the size of the ellipsoidal O 2 molecule with an
0-0 distance of 1.21 A by its charge density contour given by Bader et al. [10.22]. On this basis the
molecule is 4.18 Along and 3.18 Awide. Spectra (d) and (e) are for a monolayer ofphysisorbed O 2 on
Pt(lll), prepared at 17 K. The physisorbed molecules lie down on the surface as shown in (C), where
we have used the same relative sizes of O 2 and Pt as in (c). Spectra (g) and (h) are for a monolayer of
chemisorbed O 2 prepared by heating a physisorbed layer to 80 K. The chemical 1t bond of
chemisorbed O 2 is illustrated in (i). It involves the 1t! MO, while the 1t~ orbital remains largely
uninvolved

measurements were made at 17 K. The spectra for multilayer and physisorbed

O 2 in Fig. 10.7 strongly resemble that of gas phase O 2 (Fig. 4.14b) discussed in
Sect. 4.2.8.
Resonance 1 in Fig. 10.7 is due to a lau -+ In: transition and resonances 2
and 3 are primarily a* resonances, corresponding to spin-up and spin-down
lag -+ 3a: transitions, respectively. The splitting arises from two different final
304 to. Selected Applications of NEXAFS

state spin configurations, as shown in Fig. 3.11c and discussed in Sect. 4.2.8. In
particular, for adsorbed molecules the Rydberg contribution of resonance 3 is
expected to be broadened significantly. This is confirmed by the reduced
intensity of peak 3 relative to the gas phase ISEELS spectrum shown in Fig. 4.14
and the high resolution X-ray absorption spectrum shown in Fig. 7.18. The
observed splitting between resonances 2 and 3, most prominent in Fig. 10.7b
and d, is therefore predominantly a magnetic exchange splitting effect as
schematically indicated in Fig. 3.11c.
The assignment of the symmetry character of the resonances allows one to
unambiguously determine the molecular orientation. Since 0'* resonances have
maximum intensity for E along the internuclear axis, O 2 is oriented preferen-
tially along the surface normal in the thin multilayer, and it lies down on the
surface in both the physisorbed and chemisorbed states. The results of the curve
fits shown in Fig. 10.7, and assuming 85% linearly polarized X-rays, give tilt
angles of the 0-0 axis from the surface plane of 55° for the multilayer and < 15°
for the physisorbed and chemisorbed monolayers. The orientations determined
by the curve fits are shown schematically next to the spectra.
For lying-down O 2 , any chemical bonding to the substrate has to involve the
n system of the molecule. In fact, because there are two orthogonal n* orbitals
[10.23], as shown schematically in Fig. 10.7i, one would expect a difference
between the orbital parallel (nil) and perpendicular (n.d to the surface. NEXAFS
can distinguish between the two n* orbitals because the n* resonance corres-
ponds to a 10' --+ n~ transition for E parallel to the surface and 10' --+ n! for E
perpendicular to the surface. For physisorbed O 2 , curve-fitting of the n*
resonance gives the same width (1.37 eV FWHM) and position (530.7 eV) for
both glancing and normal incidence spectra. These values are close to those
found for the width (1.46eV) and position ([Link]) of multilayer O 2 , For
chemisorbed O 2 the n* resonance at normal incidence falls at 530.3 eV with a
width of 1.37eV while at glancing incidence it falls at [Link] and is severely
broadened with an asymmetric line shape.
These results indicate that for physisorbed O 2 there is no chemical bond to
the surface via the n* system, and the molecule-substrate interaction is of
van-der-Waals nature, as in condensed O 2 , For this reason the molecules in the
structural models in Fig. 10.7c and f are shown as ellipses with their size
determined by the charge contour which includes 95% of the total charge
density [10.22]. In contrast, for chemisorbed O 2 the energetic inequivalence of
the n* resonances at normal and glancing incidence and the asymmetric
broadening of the n* resonance at glancing incidence show a strong involvement
of the n! orbital in the molecule-substrate bond.
We attribute the broadening to a mixing of n!-Pt dn orbitals with charge
transfer of about one electron from the metal into the n! orbital, producing a
superoxide O 2 species. In a simple incorrect picture, charge transfer of a whole
electron into the n! orbital would completely fill this orbital and therefore no
corresponding NEXAFS resonance should be observed, contrary to experi-
mental observation. The observed "n!,' resonance is instead due to a transition
 10.3 Molecular Oxygen on Pt(lll) and Ag(llO) 305

to an unfilled orbital of n symmetry resulting from the hybridization of the n!

orbital with Pt dn orbitals, similar to the situation encountered for di-sigma
bonded ethylene on Pt(lll) [10.24], see Sect. 10.4.2.
For chemisorbed O 2 the nO resonance (orbital) appears to be undistorted by
the surface bond, as expected for a superoxo-like species. We attribute its shift
( ~ 0.5 eV) to lower energy as a bonding shift due to the net transfer of electronic
charge onto the molecule. This shift approximately compensates the destabiliz-
ation (higher energy) shift of the "n!" orbital induced by the interaction with the
Pt dn orbitals. The "n!" resonance position therefore remains nearly unaffected
relative to the n* position in physisorbed O 2 ,
The structural differences of the two O 2 species is revealed most dramatically
by the respective 0"* resonances (Fig. 10.7, see also Fig. 7.15). The exchange
splitting, clearly seen in the spectrum of physisorbed O 2 , is not evident for
chemisorbed O 2 , Curve fitting yields a splitting of 3.0eV for the physisorbed
species. The low energy peak at 539.6 eV is well fitted with a symmetric Gaussian
(3.1 eV FWHM) while the high energy peak at 542. 6 eV has an asymmetric
Gaussian profile, owing to the fact that it merges into the ionization continuum
above the vacuum level with an onset of [Link] [10.19]. For chemisorbed O 2
only a single pronounced 0"* resonance at 535.6eV is observed and it can be
accounted for by a single slightly asymmetric Gaussian. A weak broad feature at
higher energy (543.0eV) is attributed to scattering processes involving substrate
atoms or to multielectron effects. The fit shown in Fig. 10.7g is the simplest
possible way to account for the 0"* resonance. Fits with two Gaussians, as for the
spectrum of physisorbed O 2 , give an upper limit of the exchange splitting in
chemisorbed O 2 , if present at all, of 2.2 eV.
The reduction of the exchange splitting in chemisorbed O 2 is attributed to
the strong interaction of the n! molecular orbital with the surface. Charge
transfer from the substrate into this orbital will lead to a partial spin compensa-
tion, e.g., to a doublet ground state for an O 2 species. This initial state effect is
expected to lead to a reduced exchange splitting in the final state. Another
interesting possibility is a dynamical spin relaxation effect. In NEXAFS an
exchange splitting will only be observed if the spin relaxation time of the
electrons in the n* orbitals is longer than the lifetime of the core excited final
state. The relevant final state lifetime can be estimated from the width of the 0"*
resonance to be about 10- 16 s. Little is known about the spin relaxation time of
a paramagnetic molecule on a metal surface. From the failure of ESR ex-
periments to reveal any paramagnetic splitting for chemisorbed O 2 on Ag(llO)
[10.25] and from estimates based on spin relaxation times of magnetic impu-
rities in non-magnetic hosts [10.26] it is believed that the spin relaxation time of
a paramagnetic molecule on a surface at 20 K is shorter than 10- 12 s. It is
conceivable that while the spin relaxation time for physisorbed O 2 is long
compared to the final state lifetime, it is comparable to it or even shorter than it
for chemisorbed O 2 owing to the stronger coupling of the n electrons to the
conduction electron bath of the substrate. This would lead to a reduced or
vanishing exchange splitting of the 0"* resonance.
306 10. Selected Applications of NEXAFS

10.3.2 Chemisorbed O 2 on Ag(llO)

Figure 10.8 shows the oxygen K-edge absorption spectra for O 2 chemisorbed on
Ag(llO) at 90 K and at various polar and azimuthal E vector orientations.
Additional experiments on H 2 0, carbonate (C0 3 ), and atomic oxygen showed
that the spectra in Fig. 10.8 were not affected by these frequent contaminants for
Ag(110). Note that the shown spectra are for a surface that contained subsurface
atomic oxygen as shown in Fig. 5.26. Only one major peak, at 532.6 eV, is
observed in the spectrum which is superimposed upon the atomic-like absorp-
tion step. The peak is assigned to a transition from the 0 Is core level to the
unfilled 0"* antibonding orbital of the 0-0 bond in good accord with the K-
shell spectrum of H 2 0 2 gas [10.28]. Note that for a peroxide-like species the n*
orbital is filled and the 0"* resonance should therefore not exhibit an exchange
splitting. For Ell along the [001] azimuth and e = 90° a second weak peak is
observed around 542 eY. This feature is attributed to a scattering resonance due
to the adsorbate-substrate bond.
The 0-0 0"* peak in Fig. 10.8 is dominant in one orientation only, when the
Ell vector of the X-rays is parallel to the surface (e = 90°) and parallel to the
[110] azimuth. Since the 0"* peak is maximized when Ell is parallel to the 0-0
bond, this is also the rough orientation of the 0-0 bond. Quantitative analysis
of the angular dependence of the intensity of the 0-0 0"* peak was accomp-
lished by deconvolution of the spectra into a Gaussian peak for the 0-0 0"*
peak and a Gaussian-broadened absorption step as shown at the top of Fig. 10.8
and discussed in Sect. 7.4.3. From measurements with Ell parallel to [110] and

°2/Ag(110)

10

Fig. 10.S. Oxygen K-edge NEXAFS spectra for

[001] 90 O 2 on Ag(llO) at 90 K as a function of polar and
azimuthal Ell orientations [10.27]. The 0-0 0-*
10
peak at 532.6eV is strongest when Ell lies along
the 0-0 bond direction, which occurs when Ell
is along the [110] azimuth and parallel to the
surface (0 = 90°). The line at 529.3eV marks
520 530 540 550 560 the 0 (Is) binding energy relative to the Fermi
Photon Energy (eV) level for O 2 on Ag(110)
 10.3 Molecular Oxygen on Pt (111) and Ag(110) 307

at polar angles of 90°, 45°, 20°, and 10°, the 0-0 axis was determined to be
parallel to the surface with a maximum error of 12°. A nearly constant 22 ± 2%
remnant of the 0-0 0"* peak is observed when Ell is along any polar angle of the
[001] azimuth. As discussed in Sect. 9.5, this can be accurately accounted for by
the small E1. component of the elliptically polarized synchrotron radiation,
which for this sample orientation lies along the [1 TO] azimuth. In particular, by
use of (9.21), for R = 0.22 we obtain P = 0.82. Hence if we assume an X-ray
polarization of 82 % at the 0 K -edge, the 0-0 axis is found to lie directly along
the [110] azimuth (~ 10° uncertainty).
The absence of the n* resonance for chemisorbed O 2 / Ag(llO), signifies
complete filling of the n* orbital and a bond order of one as in peroxide (H2 O 2)
with an O~- valency. This is in contrast to chemisorbed O 2 on Pt(111), where
only one n* orbital is involved in the surface bond, and the O 2 molecule has a
bond order larger than one and a valency of O 2 . This picture is supported by
the 0-0 bond lengths determined from the data as discussed below.

10.3.3 Hybridization and Bond Length

In order to determine the 0-0 bond length in adsorbed molecules it is best to
look at spectra taken in an experimental geometry where the 0"* resonance is
largest. This is done in Fig. 10.9, where the spectra of various monolayer
adsorption systems are compared to gas phase K-shell spectra of two standards,
O 2 and H2 O 2 , representing the two extreme cases of 0-0 bond hybridization.
For physisorbed O 2 the 539.6eV position of the first 0"* resonance, which is least
affected by changes in overlapping Rydberg resonances, is similar to the values
540.0eV in multilayer O 2 and 539.3 eV for the gas phase. This indicates almost
identical bond lengths (1.21 A) in the three phases. Differences in intensity ratios
and splittings between resonances 2 and 3 are largely attributed to changes in
the Rydberg contribution of resonance 3. We also note that solid O 2 is
antiferromagnetic [10.31], which can affect the exchange splitting via the
exchange interaction between adjacent oxygens. In contrast, Figs. 10.7 and 10.9a
reveal a pronounced shift for chemisorbed O 2 on Pt(l11), ~ 5 eV, using the
centers of gravity of the respective 0"* resonances. For O 2 on Ag(llO) the shift is
even larger, ~ 8 eV.
The change of the 0"* resonance position with 0-0 bond length has already
been discussed for gas phase molecules (Sect. 8.4), and a model was presented in
Sect. 8.6.4 showing how the gas phase correlation may be transferred to the case
of chemisorbed O 2 • We shall use this idea here and assume that the bonding
shift in the gas phase in going from O 2 to H2 O 2 also applies on the surface for
chemisorbed O 2. There is evidence that this assumption is valid. In particular,
the spectra of chemisorbed O 2 on Ag(110) in Fig. 10.8 do not exhibit a n*
n;
resonance, and therefore the 1 orbital (Fig. 3.11) is filled, yielding an O~­
species. The XPS binding energy of this species relative to the Fermi level
(529.3 eV) is 1.7 eV lower than that for chemisorbed O 2 on Pt(lll), shown in
Fig. 7.15, as expected for additional electron transfer from the metal to the
30S 10. Selected Applications of NEXAFS

(a)

:>
2
(f)
c: g 538
;:;

.
~
c: iii
~ 536
t:>
Chemisorbed
°2/Ag(110) 534

532

540 545 550 555

Photon Energy (eV) 0-0 Bond Length (A)

Fig. 10.9. (a) Shift of the u* resonance for different bonding states of molecular O 2 on Pt(111)
[[Link]] and Ag(llO) [10.27] surfaces in comparison with gas phase O 2 [10.29] and H 2 0 2 [10.2S].
(b) u* resonance position, given by the vertical line position in (a), as a function of 0-0 bond length.
The straight line was established by using the gas phase data points (circles) for O 2 (double bond,
R = 1.207 A) and H 2 0 2 (single bond, R = 1.475 A) taken from (a), and for CF 30-0CF 3 (single
bond, R = 1.419 A) [10.30]

molecule (Fig. 8.9). Thus we should be able to use the correlation between the
absolute u* resonance position and the bond length for gas phase molecules to
determine the bond lengths for physisorbed and chemisorbed O 2 ,
This is done in Fig. 10.9b, where we have superimposed the u* resonance
positions for the three O 2 phases on Pt(111) and Ag(110), taken from Fig. 10.9a,
on the gas phase correlation curve, taken from Fig. 8.9. Use of the linear
correlation, shown as a solid line, predicts significant bond lengthings to
1.37 ± 0.05 A for chemisorbed O 2 on Pt(111) and 1.48 ± 0.05 A for chemisorbed
O 2 on Ag(llO). The relatively large error bars of ±0.05A are rather conserva-
tive and include various sources of possible errors. Using the curved inter-
polation function, shown dashed, which more closely follows the expected 1I R2
behavior discussed in Chap. 8, we obtain 1.35 A for chemisorbed 02/Pt(I11)
and 1.49 A for chemisorbed 0 2 1Ag(llO). We believe these values are more
reliable, yet they should still have error bars of ± 0.05 A.
The distances for chemisorbed O 2 on Pt(I11) and Ag(llO) correlate well
with trends in dioxygen bonding to transition metals [10.32, 33]. For example,
in his review Hall [10.34] gives values of 1.34 A for a typical 0-0 bond length
for the superoxide 02' ion (bond order 1.5) and 1.49 A for the peroxide O~ - ion
(bond order 1). Although no reliable data are available as to the chemisorption
 10.4 The Bonding of Simple Hydrocarbons on Metals 309

(a) 02/Ag(110) (b) 02/Pt(111)

[001] t

Fig. 10.10. Proposed structural models for chemisorbed O 2 on Ag(llO) and Pt(lll). Note that the
O 2 position (filled circles) on Ag(llO) places it in the troughs such that it can bond to the atoms in
the second Ag layer, directly underneath, as well as to the Ag atoms flanking it in the first layer. The
shown orientation has been determined by NEXAFS and the position is favored by electronic
structure calculations [10.35]. The 02/Pt(lll) geometry is suggested by unpublished SEXAFS data
[10.36]

geometry of O 2 relative to the underlying substrate atoms on the Ag(110)

and Pt(l11) surfaces, we show in Fig. [Link] two likely configurations. For
02/Ag(1l0) the shown orientation of the 0-0 axis was determined by
NEXAFS. By positioning the O 2 molecules in the troughs between two rows of
Ag atoms both nO and n! orbitals may interact with Ag atoms, located beside
and underneath the molecule, respectively. This geometry thus favors formation
of a peroxide-like species. The 02/Pt(111) geometry shown in Fig. to.10b has
O 2 lying down as determined from NEXAFS and the shown geometry is
suggested by unpublished SEXAFS results [10.36].
The interaction of O 2 with Pt(lll) and Ag(llO) is a textbook example of a
n*-acceptor bond. The charge transfer into the n* orbitals causes a rehybridiz-
ation and lengthening ofthe intra-molecular 0-0 bond, and for O 2 on Ag(llO)
an azimuthal alignment of the molecule. In contrast to CO, O 2 prefers a lying
down geometry. This is simply understood by the fact that the HOMO is a n
(lnu) orbital in O 2 while it is a (1 (5(1) orbital in CO [10.37]. Thus the n-donor
component of the chemisorption bond stabilizes the lying-down geometry.

10.4 The Bonding of Simple Hydrocarbons on Metals

Of the many chemisorption systems involving di-carbon species, the C2 di-

atomic on Ag(llO) [10.38, 39] and the C2H 4 molecule on Pt(l11) [10.24,40]
exhibit particularly noteworthy NEXAFS spectra. In both cases the experi-
mental spectra have been interpreted by means of self-consistent cluster calcu-
lations. The results of these calculations are of fundamental importance for the
interpretation ofNEXAFS spectra in general, in that they point out the effects of
strong molecule-metal bonding.
310 10. Selected Applications of NEXAFS

It is shown below that the bond to the surface may cause the disappearance
of certain gas phase resonances in the NEXAFS spectra and/or the appearance
of new kinds of resonances. The new molecule-metal resonances are associated
with transitions to unfilled molecule-metal orbitals and give additional informa-
tion on the details of the chemisorptive bond. Furthermore, their mere existence
is of interest since we had previously concluded in Sect. 6.2 that such resonances
should be weak or severely lifetime broadened. Secondly, the calculations reveal
the effects of lowering the molecular symmetry in a chemisorption complex
relative to that of the free molecule. This has important implications for the
general interpretation of the polarization dependence of NEXAFS resonances.
The present studies provide specific examples for the general discussion of
symmetry lowering effects given by Somers et al. [10.41].
We shall first discuss C 2 on Ag(llO) because of its close link with the O 2
species on Ag(llO), dealt with in Sect. 10.3.2.

10.4.1 Bonding and Orientation of C2 on Ag(llO)

The diatomic C 2 species and its ions C; and C;: have been prepare.d and
characterized in the gas phase. Their bond lengths are 1.243 A, 1.30 A, and
1.268 A, respectively [10.42] and their molecular orbital structure is similar to
that of N2 and O 2, schematically shown in Fig. 3.1. This orbital ordering is
preserved in C; and C;: [10.43,44]. When the 12 electrons of C 2 are filled into
the molecular orbitals in that figure, the HOMO is seen to be the lnu and the
LUMO is the 30"g. The (lnu)4(30"g)O electronic configuration for C 2 has been
found to be only slightly (~0.0geV) lower than the (lnu)3(30"g)1 configuration
[10.45].
The C 2 species can also be prepared on the Ag(llO) surface by sequential
dehydrogenation of acetylene (C 2H 2) [10.46]. On the clean Ag(llO) surface
acetylene chemisorbs below 150 K into a weakly bonded molecular state that
desorbs at 195 K. In the presence of preadsorbed atomic oxygen, C 2H2 is
dehydrogenated to C 2H with H 20 gas formation near 170 K and C 2H decom-
poses into acetylene gas and chemisorbed C 2 near 275 K [10.46].
The polarization-dependent NEXAFS spectra for C 2 on Ag(llO) are shown
in Fig. 10.11. The 0"* resonance is most pronounced and the n* resonance is
smallest when the E vector is parallel to the surface and along the [110]
azimuth. Hence the C-C axis lies approximately along the troughs of Ag atoms,
just like the 0-0 axis for 02/Ag(1l0), as shown in Fig. 10.10a. A quick estimate
of the C-C bond length using a 0"* resonance position of 304 eV and the plot in
Fig. 8.23 yields a value of 1.285 A, which is similar to the values listed above for
gas phase C 2 and its ions. The precision of the derived bond length is too low
( ± 0.05 A), however, to make a definitive determination of the oxidation state of
C 2 on Ag(llO).
An interesting point is the large width of the n* resonance, which appears to
have several" components. For example, for E parallel to the surface and along
the [001] azimuth (top spectrum in Fig. 10.11a), there appears to be a narrow
 10.4 The Bonding of Simple Hydrocarbons on Metals 311

C 2/ Ag (110)
~'-~-r~-.~-.--~.-~ ~~~--r-r-.-~,-~~~

(a) TT · (b ) E
+~
(001) [O~§
S§

(110)
--a::o
<XX>
E

280 300 310 320 280 290 300 310 320

Photon Energy (eV)

Fig. 10.11. Polarization-dependent NEXAFS spectra of 0.25 monolayers ofC 2 on Ag(l 10) recorded
at 80 K for normal (a) and 20° grazing (b) X-ray incidence [10.38, 39]. All spectra have been
normalized to the same edge jump. The azimuthal orientation of the E vector for each spectrum is
indicated by icons. The XPS binding energy relative to the Fermi level (282.8eV [10.46]) is marked
FL. In (a) we have also indicated as a dashed line a step function and two Gaussian components,
which are distinguished by their shading. The experimental intensity in the 285- 290eV region can be
quantitatively accounted for by the step function and the Gaussians

central component, at an energy of 286.4 eV. This component is reduced relative

to the higher energy component around 288.0eV when the azimuth is rotated by
90° (bottom spectrum in Fig. [Link]). We have tried to indicate these two
possible components in Fig. lO.1la by two differently shaded Gaussians which
have the correct intensity and width to fit the experimental intensity in the
285-290eV region when added to the step-like background, shown dashed. At
grazing X-ray incidence only a broad "n*" peak is observed without any
discernible components (Fig. [Link]).
In light of the molecular orbital scheme of C z it is surprising that no
resonance associated with the lowest energy lau -+ 3ag transition is observed,
which from gas phase calculations [10.45] should appear 5-lOeV below the n*
resonance. This resonance is indeed found in the calculation of the NEXAFS
spectrum for gas phase C z , shown in the left column of Fig. 10.12. The shown
calculation by Stevens et al. [10.39] was carried out for an oriented gas phase C z
species with a bond length of 1.24 A, using the ab initio Stieltjes- Tchebycheff
method discussed in Sect. 2.8. For E perpendicular to the C-C bond axis a
pronounced n* resonance and weak Rydberg resonances are observed, as
expected. For E along the C-C axis the lowest energy resonance, marked 3ag,
corresponds to the expected lau -+ 3ag transition, and the a* shape resonance
above the IP corresponds to the lag -+ 3au transition (Fig. 3.1).
312 10. Selected Applications of NEXAFS

t
Free C2 C2 /A9 6 (110)
60
,,' 60
[ 1101 (d)
C C(a)

50 50
".i
~
~
Rydberg IC,·Agl '

I
"'E
u
co
';"0 ~k
,,'
~
40 ~ ~O~

etc
(b) 40 [00 1) (e)
0
,,'II
ec
~
.D

0
.~ 30 30
CI)
</)
Rydberg
e
</)
(C,·AgI'

0
0
c
/ ..
,' -
20 20
.~
30g (e)
lil ( 1101 (f)

cS
.D
ro
0
C c•
(5
.<=
a.. 10 10

o
-20 0 20 ·20 0 20
Excitation Energy Relative to Ionization Potential (eV)

Fig. 10,12. Stieltjes- Tchebycheff molecular orbital calculation of the polarization-dependent K-

shell excitation spectra of free C 2 (a-i:) and a C 2 1Ag 6 (110) cluster [10.39]. The orientation of the E
vector relative to the C-C bond is shown in each case, and in (d- f) the E vector orientation is given
above the icons. For the gas phase the spectra in (a) and (b) are identical by symmetry. All spectra are
plotted on the same vertical scale with a vertical offset by 20 Mb for (b) and (e) and 40 Mb for (a) and
(d). The origin of the resonances is discussed in the text. Note that the black 3170 resonance
disappears for the chemisorbed case and new types of resonances, marked (C 2 -Ag)* and shown with
a dotted shading, appear

The corresponding polarization-dependent calculation for chemisorbed C 2

on Ag(11O), modelled by a C 2 1Ag 6 (110) cluster, is shown for comparison in the
right column of Fig. 10.12. The ground state geometry of chemisorbed C 2 was
first determined using a 24 Ag atom cluster model by a generalized valence bond
calculation that included the effects of configuration interaction, as previously
published for O 2 on Ag 24 (11O) [10.35]. C 2 was found to occupy the long bridge
site above the troughs, with the C-C axis parallel to the surface and in the [110]
direction, as shown for O 2 in Fig. 10.10a. The C-C distance was found to be
1.29 A, and the molecule to sit 1.06 Aabove the surface plane.
The most pronounced change upon adsorption occurs when the E vector is
aligned along the C-C axis, i.e., between Fig. 1O.l2c and 1O.12f. The pronounced
 10.4 The Bonding of Simple Hydrocarbons on Metals 313

30' g resonance in the gas phase spectrum, shown in black, is absent in adsorbed
C 2. In contrast, the 0'* shape resonance is observed in both cases. The disap-
pearance ofthe 30'g resonance for chemisorbed C 2 arises from charge transfer of
electrons from the surface into the 30'g orbital. Because this orbital is formally
full for C 2 on Ag(llO), as shown by generalized valence bond calculations,
electrons from the K-shell cannot be excited into it. This situation resembles that
for 02/Ag(1l0), where the transfer of metal electrons caused the filling ofthe lng
antibonding orbital [10.35]. For C 2, however, the transfer is into the bonding 30'g
orbital. The nature of the MO involved in the backbonding has important
consequences for the intra-molecular bond length. For example, the 0; species
(:~d.35 A) shows a 0.14 A bond length increase relative to ground state O 2
(1.21 A), while free C; (1.27 A) is only about 0.03 A longer than neutral C 2
(1.24A). Although the 30'g orbital is formally filled in chemisorbed C 2, the net
charge on the C 2 species is most likely less than two electrons due to a synergetic
bonding-back bonding charge transfer.
At first sight the calculations for E perpendicular to the C-C axis look
similar for free C 2 (Fig. 10.12a, b) and for chemisorbed C 2 (Fig. 10.12d, e).
However, there is an important difference. In addition to the n ~ resonance
observed for E parallel to the surface, and the n! resonance observed for E
perpendicular to the surface, a second resonance, marked (C 2-Ag)* is observed.
This resonance, shown with dotted shading, is more intense than the Rydberg
resonances in the calculated gas phase spectra. It actually consists of several
components, indicated by its shifting position as a function of polarization. The
resonance is also observed for E along the C-C bond direction, and hence has to
contain some 0' character.
While the new (C 2-Ag)* resonances observed for chemisorbed C 2 are close
in energy to the Rydberg resonances in the gas phase spectrum, they are quite
different in character. This is beautifully shown by the charge contour plots in
Fig. 10.13. In the left column we show the charge contours of the In: orbital
which is associated with the n* resonance and of the Rydberg orbital which
gives rise to the corresponding resonance in the C 2 spectra in Fig. 10.12a and b.
In the right column we show the n! orbital and the (C 2-Ag)* orbital which both
lie in a plane which is perpendicular to the surface and along the [1 10] direction.
These orbitals give rise to the n! resonance in Fig. 1O.12d and the (C 2-Ag)*
resonances in Fig. 10.12d and f. Comparison of Fig. 10.13a and c shows that the
n * orbital is only weakly perturbed by the interaction with the surface. In
contrast, the Rydberg orbital in Fig. 10.13b is substantially different from the
(C 2-Ag)* orbital in Fig. 10.13d. For example, it does not have the large spatial
extent of a Rydberg orbital.
Another interesting point about the (C 2-Ag) * orbital is that it is of "mixed 0'
and n symmetry", indicating that for the chemisorbed case these symmetry
labels have lost their meaning. The symmetry reduction is a consequence of the
strong interaction with the surface. The composition of the (C 2-Ag)* orbital
shown in Fig. 10.13d can be formally written as (lnJ. + 30'g - (p(Ag». Close
inspection of the (C 2-Ag)* orbital contour in Fig. 1O.13d reveals that the
314 10. Selected Applications of NEXAFS

Fig. 10.13. Orbital contour

(a) (e) plots of various orbitals associ-
ated with some of the strong
TT' TT'
1. transitions in Fig. 10.12 [10.39].
4.0 The labelling is the same as in
that figure. The contours run
2.0 from -I to I in steps of 0.01.
Results for free C 2 are shown in
the left, and results for
0.0
C 2 / Ag 6 (110) in the right col-
umn. For the adsorbed species
- 2.0 the plotting plane is perpendi-
cular to the surface, along the
- 4.0 1-_..l....:::::=-....L..=....L..._-/-_---'-_ ---'_ _'-----j [110] direction. The two Ag at-
€ (d ) oms are the second layer trough
0' atoms underneath the molecule,
as shown in Fig. [Link]

directions of maximum orbital density near the C nuclei, indicated by two

straight lines, are neither parallel nor perpendicular to the surface, and they are
also not directed along the C-Ag axes. Since the polarization dependence of
NEXAFS resonances is determined by the dipole pattern of the corresponding
valence orbital near the 1 s core, the 1 s -+ (C 2 -Ag)* transition, associated with
the orbital shown in Fig. l0.13d, would have an angular dependence determined
by the directions of the lines in that figure. Hence the transition would be
observed for both E parallel and E perpendicular to the surface. This is
<:onfirmed by comparison of the calculated spectra in Fig. 10.l2d and f.
We have purposely used a specific shading of the resonances in the experi-
mental spectra in Fig. 1O.11a and the corresponding calculated spectra in
Fig. 1O.12e and f in order to indicate a correlation. The broad "n*" resonance in
the experimental spectra is thus predicted to consist of a conventional n*
resonance plus a (C 2-Ag)* resonance at higher energy. At normal X-ray
incidence (Fig. lO.l1a) the n* component arises from the n~ orbital, while at
grazing incidence (Fig. l0.11b) the n! component dominates. As for chemi-
sorbed O 2 on Pt(lll), the measured resonance at grazing incidence, associated
with the n! orbital, is broader because of orbital overlap with the surface. This
broadening effect is not included in the calculation, which assumed a constant
 10.4 The Bonding of Simple Hydrocarbons on Metals 315

2.0 eV FWHM for all bound state transitions. Although the n ~ orbital is
oriented along the [001] direction, the corresponding transition (dashed shad-
ing) is still seen in the bottom spectrum in Fig. lO.11a because of the finite
nonlinear X-ray polarization (Sect. 9.5).
The strong broadening effect in the "n *" resonance upon chemisorption
observed here for C 2 on Ag(llO) is not an isolated result. We shall see below,
e.g., for phenyl-ring based molecules bonded to Mo(llO), that such effects are
quite common in unsaturated hydrocarbons, whenever the interaction with the
surface is strong.

10.4.2 Di-sigma Bonded C 2 H 4 on Pt(111)

The interaction of ethylene with Pt(lll) surfaces produces several phases as a
function of temperature. Below about 50 K, the molecule is physisorbed [10.47]
and transforms into a chemisorbed species at T> 55 K. Chemisorbed ethylene
was found to lie down on the surface by electron energy loss spectroscopy
(EELS) [10.48] and to exist up to about 250 K, when it transforms into standing
up ethylidyne (H3C-C ==) [10.49, 50]. Ethylene and ethylidyne on Pt(lll) were
also investigated by NEXAFS spectroscopy in 1984 by Koestner et al. [10.40]
and these results were reinterpreted in 1985 by Horsley et al. using XIX-MS
calculations [10.24]. Below we shall review the NEXAFS results for ethylene
chemisorbed on Pt(l11) at 90 K.
Two types of configurations have been used to describe the bonding of
ethylene to metal surfaces. The first one is similar to that in the organometallic
complex known as Zeise's anion, [PtC 2 H 4 Cl 3] -, where ethylene n-bonds to a
single Pt atom with C-Pt and C-C bond lengths of 2.13 Aand 1.37 A, respect-
ively [10.51, 52]. In this n-bonding configuration ethylene is Sp2 hybridized with
only a 0.03 A lengthening of the C-C bond relative to the gas phase. The second
configuration is that found in the ethane di-halides C 2 H 4 X 2 , where X = F, Cl,
Br or I. In this di-sigma configuration the molecule is Sp3 hybridized, similar to
ethane, with a bond length close to 1.53 A [10.53]. On the surface this configura-
tion would involve bonds of each C atom with Pt surface atoms in a local
C 2 H 4 Pt 2 arrangement.
This latter bonding configuration was originally suggested for the C 2 H 4 on
Pt(lll) system by Steininger et al. [10.48] from a comparison of EELS vibra-
tional frequencies of C 2 H 4 on Pt(l11) with those of C 2 H 4 Br 2 and Zeise's anion.
The experimental NEXAFS spectrum, corrected for a sloping background
[10.24], is shown in the left panel of Fig. 10.14. It is discussed in Sect. 8.6.3 in
conjunction with Fig. 8.22 and consists of a peak X, close to the 285 eV position
of the n * resonance in the free molecule, and a (J * resonance around 293 eV. The
existence of the n*-like resonance X led Koestner et al. [10.40] in a preliminary
interpretation of the spectra to propose that ethylene was bonded in a n and not
a di-sigma conformation, in contrast to the conclusions of the EELS study. In
order to resolve this discrepancy Horsley et al. [10.24] calculated NEXAFS
spectra by means of the XIX-MS method for both configurations.
316 10. Selected Applications of NEXAFS

Experiment Xa-MS Theory

I q' q'
C 2 H 4/Pt(111)
90K
X
0.25
I
E~90°
~C ~
I \
PI PI
0.151-L...- - - - - - - '

en
::::!;
~ 0.05
<::
<:: .2
e
o
oQl
(fJ
Ql
iii '" 0.25
"iii ()
e'"
§ 0.15
o

'r---
Z

.........._-' ~xPs 0.05 \

,
I
I

290 310
""o 10 20
Photon Energy (eV) Energy from IP (eV)

Fig. 10.14. Experimental NEXAFS spectrum for C 2 H .. on Pt(lI!) at 90 K in comparison with that
calculated by means of XIX-MS theory for a C 2 H4 Pt 2 cluster [10.24]. For the calculation the C-C
bond length was assumed to be 1.50 A and the molecule was distorted appropriate to Sp3
hybridization. In this geometry ethylene is said to be di-sigma bonded. Both the CCH and CCPt
angles were fixed at 109S. This yielded a Pt-C distance of 2.1 A when using the bulk internuclear
Pt-Pt distance of 2.77 A. The contour plot ofthe lowest unoccupied biorbital ofthe Pt 2 C 2 H 4 cluster
is shown in an inset. This orbital is associated with the resonance marked X

The results of these calculations for the di-sigma configuration are shown in
the right panel in Fig. 10.14. The cluster taken to represent the surface complex
consisted of two Pt atoms separated by the bulk internuclear distance (2.77 A),
bonded symmetrically to an ethylene molecule with the C-C axis parallel to the
Pt-Pt axis. The ethylene molecule was distorted to a geometry appropriate to an
Sp3 hybridized molecule. The C-C bond length was taken to be 1.50 A, as
indicated by the CT* resonance position (Fig. 8.23). The hydrogen atoms were
raised above the C-C axis so that the CCH angle was 109S. The CCPt angle
was also fixed at 109S, which gave a reasonable Pt-C distance of 2.1 A.
The remarkable agreement between experimental and calculated spectra in
Fig. 10.14 led Horsley et al. [10.24] to conclude that the molecule is indeed
bonded in the di-sigma configuration as proposed by EELS. Note that the main
discrepancy between experiment and theory lies in a step-like background that
underlies the spectral region above resonance X. We have encountered this
effect before, e.g., for the C0 3 spectra in Fig. 6.26b, and it is ascribed to
transitions to states hybridized with metal states above the Fermi level, as
discussed in Sect. 7.4.3. Because of the limited cluster size this step is not present
in the calculated spectra. Evidently the 1t * orbital of free ethylene retains its
identity even in a molecule bonded in a di-sigma configuration. This can clearly
 10.5 The Bonding of Phenyl-Ring-Based Molecules to Metal Surfaces 317

be seen from an orbital contour plot of the lowest unoccupied biorbital

obtained in the self-consistent XIX calculation of the cluster, shown in the inset in
Fig. 10.14. The transition to this orbital gives rise to resonance X.
The p-like components of the biorbital on the C atoms resemble the n*
orbitals in free ethylene. Close inspection reveals that the p-like components are
not exactly perpendicular to the C-C axis, however. They are rotated in the
direction of the C-Pt axis. This indicates a symmetry lowering for the chemisor-
bed relative to the free molecule, similar to that discussed for the C 2 1Ag(llO)
system. In analogy to the (C 2 -Ag)* orbital discussed earlier we may therefore
refer to the biorbital also as a (C 2-Pt) * orbital. The origin of this orbital is best
understood as a mixing of the n* orbital of the free molecule with d-like orbitals
on the Pt atoms. This interaction leads to the formation of two delocalized
orbitals, of which the antibonding one is shown in Fig. 10.14. The fact that the
p-like component of the biorbital is not exactly perpendicular to the C-C axis
gives rise to the small resonance intensity for E parallel to the C-C axis in the
calculated spectrum in Fig. 10.14.
Calculations for C 2 H 4 n bonded to a single Pt atom as in Zeise's anion were
also carried out by Horsley et al. [10.24] assuming a stretched bond length of
1.50A. The calculated spectra were very similar to those shown in Fig. 10.14. The
argument for a di-sigma bonded geometry made by Horsley et al. therefore
hinged mainly on the 1.50 A bond length derived from the position of the 0' *
resonance. They argued that the bond length for a n bonded species should in
fact be close to that in Zeise's anion (1.37 A), which is considerably shorter than
that predicted from the NEXAFS spectra.
The above example and the results for the previously discussed C 2 1Ag(110)
system show convincingly the value of cluster calculations for the interpretation
of NEXAFS spectra of strongly chemisorbed molecules. In such cases care has
to be exercised in the interpretation of the angular dependence of the resonance
intensities because the selection rules for the unperturbed molecular symmetry
may no longer apply. This point has also been made by Somers et al. [10.41,54]
in their discussion of the role of symmetry and selection rules in the analysis of
NEXAFS spectra. In some cases complications may arise from symmetry
lowering effects associated with the "rotation" of gas phase orbitals caused by
the chemisorption bond, as in C 2 H 4 /pt(111). In other cases the creation of new
molecule-substrate orbitals may give rise to resonances that overlap in position
with "unperturbed" resonances, as for the C 2 1Ag(llO) system.

10.5 The Bonding of Phenyl-Ring-Based Molecules

to Metal Surfaces

10.5.1 General Comments

The chemistry of the six-membered phenyl ring has been of interest ever since it
was first proposed by Kekule von Stradonitz in the last century. In fact, it is hard
to imagine the field of organic chemistry without this elementary molecular
318 10. Selected Applications of NEXAFS

building block. Below we shall take a look at the bonding of molecules based on
this aromatic group to metal surfaces. In particular, we shall discuss molecules
such as benzene (C 6 H 6 ), pyridine (CsHsN), toluene (C 6 H sCH 3), aniline
(C 6 H sNH z ), phenol (C 6 H sOH), and benzenethiol (C 6 H sSH) bonded to noble
and transition metal surfaces.
In a simple-minded picture one may envision several types of interactions of
such rings on surfaces, in analogy to organometallic complexes [10.2], as
illustrated in Fig. 10.1S. In all cases we have schematically indicated the bonding
interaction as a dotted line. In rings with an unreactive end group U, the most
likely bonding arrangement will involve the n system of the ring, as discussed for
metal-ethylene bonding in Sect. 6.1.1 and indicated in Fig. 10.1Sa. Benzene itself
is such a molecule with V representing a hydrogen atom. Other examples are
rings where V characterizes attached -CH3 (toluene), -NH z (aniline), or -OH
(phenol) groups that have not been activated by dehydrogenation. In the case of
a reactive end group R, a direct (j bond to the surface via this group is possible,
as indicated in Fig. [Link]. An example is pyridine, which has a lone pair orbital
on the N atom, or a molecule with a dehydrogenated end group, e.g., phenyl-
methylene (C 6 H sCH z-) or phenylthiolate (C 6 H sS-), It could also be envisioned
that upon cracking of a C-H bond in the ring a direct carbon-metal (C-M)
bond is formed as shown in Fig. [Link]. Here we have used "X" to indicate a

la) 1t-Bond Ib) Reactive-End Bond

u--e :~
;
R
P
Ie) Carbon-Metal Bond Id) Intermolecular Bond

x~
o ;

Fig. 10.15. Schematic bonding arrangements of phenyl-ring-based molecules on surfaces. The

labels "U", "R" and "X" denote end groups that are unreactive, reactive, or of unspecified
reactivity, respectively. The bonding interaction in each case is indicated by a dotted line. (a) n-
bonding configuration, resulting in the molecular plane being parallel to the surface. (b) Typical
bonding geometry when the molecule-surface bond is via a reactive end group "R". The ring plane is
expected to be at a finite tilt angle with respect to the surface. (c) Dehydrogenation of the phenyl ring
will typically lead to the formation of a carbon-metal bond. Because of the stiffness of the aromatic
ring and the direction of the original C-H bond the molecule is expected to "stand up" on the surface
as shown. (d) At higher adsorbate coverage, interactions between the individual molecules may
become important. Such interactions are of van-der-Waals nature, often involving contributions
from hydrogen-hydrogen bonding. For a single chemisorbed layer, this interaction will typically
lead to a more "standing-up" geometry, allowing a higher packing density
 10.5 The Bonding of Phenyl-Ring-Based Molecules to Metal Surfaces 319

possible end group, which could be either unreactive or reactive. Finally, as

shown in Fig. 1O.15d, one also needs to consider the interactions between
molecules, which are typically van-der-Waals interactions with involvement of
hydrogen atoms [10.55]. We shall show below that there is indeed evidence for
the various interactions.
It is apparent from Fig. 10.15 that the various types of bonding effects may
lead to preferential orientations of the phenyl-ring plane. Clearly, an-bonded
species would lie flat on the surface to maximize the overlap of the molecular n
orbitals and the n-like orbitals of the surface metal atoms. A reactive end group
may be expected to lead to a tilted ring configuration as indicated in Fig. 10.15b.
For example, in phenoxide (C 6 H sO-) the strongly directional O-H bond in the
unperturbed molecule may simply be replaced by a O-M bond in the same
direction upon chemisorption. Similarly, formation of a carbon-metal bond, as
in Fig. 10.15c, is expected to result in a ring orientation nearly perpendicular to
the surface plane because the direction of the C-H bonds in the unperturbed
molecule is in the ring plane. Van-der-Waals interactions should exhibit a strong
coverage dependence, and therefore a strong dependence of molecular orienta-
tion with coverage is predicted. Because of its sensitivity to the molecular
orientation, NEXAFS is a technique well suited to test these simple ideas.
The first demonstration of the power of NEXAFS for the study of aromatic
rings was given in 1983 by Johnson et al. [10.56] in a study ofthe orientation of
benzene, pyridine, and toluene on Pt(lll). Since then many molecular rings
bonded to surfaces have been studied as summarized in Appendix B. Let us first
discuss the results for benzene bonded to noble and transition metal surfaces,
in particular, Pt(l11) [10.56,57], Mo(llO) [10.58,59], Ag(llO) [10.59,60], Cu(llO)
and Cu(lll) [10.61].

10.5.2 Benzene
Spectra for submonolayer benzene on Ag(llO) adsorbed at 100 K, and a
monolayer of benzene on Mo(llO), obtained by adsorbing a multilayer at 100 K
followed by heating to 200 K, are shown in Fig. 10.16. Submonolayer spectra of
benzene on Mo(llO) produced at 100 K without annealing exhibited results
identical to those shown in Fig. 10.16. The origin of the various resonances is
discussed in Sect. 6.4.4, and NEXAFS spectra of benzene in the gas phase,
condensed, and chemisorbed on Ag(110), are shown in Fig. 6.28. The polariza-
tion dependence of the resonances clearly show that in both cases the molecules
bond with their ring plane parallel to the surface, in good accord with the
n-bonding model in Fig. 1O.15a.
Despite the similar orientation of benzene on the two surfaces the spectra
exhibit significant differences in the width of the n* resonances and the position
ofthe 0'* resonances. Results for benzene on Cu(llO) and Cu(lll) [10.61], not
shown here, resemble those for Ag(llO), and the published Pt(lll) spectra
[10.56, 57], also not shown here, are similar to those for Mo(llO). For the
transition metals Pt and Mo the two n* resonances, clearly seen for Ag(llO) and
320 10. Selected Applications of NEXAFS

Chemisorbed Benzene

Ag(110)
[110[
c

@-""l
2
U
~
w

r-~ _ _~Mo(110)

Photon Energy (eV)

Fig. 10.16. Comparison of the polarization-dependent (20 and 90° X-ray incidence angles, respect-
0

ively) NEXAFS spectra of weakly bonded benzene on Ag(110) [10.59] and strongly bonded benzene
on Mo(110) [10.58]. Note that the (110) face offcc Ag(110) is rather open, while it is close-packed for
bcc Mo(110), as shown in the insets. The C6H6/Ag(110) spectrum corresponds to a coverage of
about one half of a saturated monolayer [10.60] produced by dosing the crystal at 100 K without
annealing. The C6H6/Mo(110) spectrum was recorded for a saturated monolayer by dosing a
multilayer at 100 K followed by an anneal to 200 K. For both Ag(110) and Mo(110) the angle of
incidence was changed by rotation about the [II0] axes. The XPS binding energies relative to the
Fermi level, 284.0eV for Mo(110) and 284.7eV for Ag(llO), are also indicated

Cu(llO), are not resolved. Only a broad feature between 284eV and 290eV is
observed. This can be attributed [10.59] to the stronger interaction of benzene
with the transition metals. The resulting strong hybridization of molecular rc*
orbitals with metal d-rc orbitals leads to the formation of new unfilled "rc*"
states with a broader energy distribution, as discussed for C 2 on Ag(llO) in Sect.
10.4.1. The formation of such new states arising from rc-metal bonding have been
observed in the gas-phase ISEELS spectra of metallocene sandwich compounds
M(CsHsh with metals M = Fe, Co, and Ni, and are qualitatively predicted by
extended Hiickel theory [10.62].
This initial state broadening effect may be accompanied by a final state effect
associated with the X-ray absorption process. Because the "rc*" orbital for
strongly chemisorbed benzene contains metal character, the excited photo-
electron in this orbital can decay into the conduction band of the metal. In
contrast to the gas phase or the case of weak chemisorption, where the electron
remains trapped in the unperturbed rc* orbital of the molecule, the total lifetime
of the final state given by (2.16) is then dominated by the electron lifetime and
not the hole lifetime. Thus a lifetime broadening of the rc * resonance results.
 10.5 The Bonding of Phenyl-Ring-Based Molecules to Metal Surfaces 321

It is apparent from Fig. 10.16 that the "n*" resonances do not disappear
completely at normal X-ray incidence, as expected for a lying-down ring. For
benzene on Ag(110) the residual n* peak at 285.4eV is very small at normal
incidence, and it may be superimposed on an absorption step corresponding to
transitions to states above the Fermi level. This step is expected at the XPS
binding energy 284.7 eV [10.60] and there is indeed an intensity increase at that
energy in Fig. 10.16. Liu et al. [10.59] proposed that the remaining small n*
intensity at normal X-ray incidence is most likely due to a minority species
( ~ 3 %) which may be adsorbed at steps or defect sites in a tilted configuration.
This may be anticipated for an open (110) surface of a fcc metal (see inset of
Fig. 10.16), especially for Ag(llO), which is typically characterized by a fuzzy
LEED pattern indicative of surface disorder. The broad, left-over structure in
the 286-290eV range can be attributed to transitions to C-H* orbitals, which,
because they lie in the ring plane, have the same polarization dependence as the
higher energy C-C CT* resonances, and are therefore preferentially excited at
normal X-ray incidence. For benzene on Mo(110), the broad "n*" structure in
the 284-290eV range remaining at normal X-ray incidence is slightly more
pronounced and has a step-like appearance. In particular, the inflection point of
the initial step coincides within experimental accuracy with the XPS binding
energy relative to the Fermi level, 284.0 eV [10.58]. Some intensity probably
arises from transitions to C-H* orbitals, as for benzene on Ag(110).
For benzene on Mo(llO) the left-over intensity in the 284-290eV region at
normal incidence may arise from the strong interaction of molecular n* orbitals
with metal states around the Fermi level. This interaction would lower the
molecular symmetry, i.e., from D6b to C 6v , and lead to a possible reduction in
the angular dependence of the n* transitions because excitations to both
n *(e 2 u!e 2 ) and n *(b 2g /b 1 ) final states are dipole allowed for E parallel as well as
perpendicular to the ring plane. One way this can be visualized is that through
interaction with the surface the "n *" orbitals of the chemisorbed molecule may
no longer be perpendicular to the ring plane. Such effects are discussed in Sect.
10.4 for C 2 H 4 /Pt(111) and C 2 1Ag(110).
The difference in molecule-surface interaction revealed by the n* resonance
width is confirmed by the temperature programmed reaction behavior of
benzene on Ag(llO) and Mo(llO). On Ag(llO), benzene only undergoes desorp-
tion during heating, with a desorption maximum at about 250 K for saturation
initial coverages [10.59]. On Mo(110), on the other hand, chemisorbed benzene
remains intact up to nearly 350 K before undergoing competing desorption and
decomposition reactions. Kinetic analysis of the desorption line shape for
saturation initial coverages of benzene on Ag(110) gives a value for the activa-
tion energy for desorption of 10 kcal/mole, which compares to 22 kcal/mole for
benzene on Mo(110) [10.59].
The stronger chemisorption bond of benzene on Mo(110) also affects the a*
resonance positions. Whereas the two a* resonances for benzene on Ag(llO) are
unshifted from those in the gas phase and multilayer spectra (Fig. 6.28), there is
about a 1 eV downward shift of the first and a 2eV downward shift of the second
322 10. Selected Applications of NEXAFS

0"* resonance. Qualitatively, this suggests a ring expansion for benzene on

Mo(110). Because of the 0"* resonance splitting caused by conjugation, a
quantitative determination of bond lengthening is difficult without a model
calculation. Also, there is uncertainty whether the ring expands symmetrically or
distorts into bonds with alternating lengths, as might be indicated by the
unequal shift of the two resonances. Let us nevertheless make a rough estimate.
We assume an average shift of 1.5 eV to lower energy, and use the slope of the
C-C line in Fig. 8.7, namely a resonance shift of 5.5 eV for a 0.1 Achange in bond
length, as our calibration. This yields an average bond lengthening for benzene
on Mo(110) of 0.03 A, a rather small value. Considerably larger symmetric
expansions or asymmetric distortions into a cyclohexatriene structure have been
suggested from LEED studies for benzene on other transition metal surfaces
[10.63].

10.5.3 Phenyl Thiolate and Phenoxide

NEXAFS spectra of phenyl rings with reactive end groups are shown in
Fig. 10.17. The polarization dependence of the spectra of phenyl thiolate
(C 6 H sS) on Mo(110) [10.64,65] and of phenoxide (C 6 H sO) on Mo(110) pre-
covered with one third of a monolayer of atomic oxygen [10.66] shown in
Fig. 10.17a and b, respectively are remarkably similar. Phenyl thiolate was
prepared by dosing the clean Mo(110) surface with a multilayer ofbenzenethiol
at lOOK and annealing it to 200K. The phenoxide layer on O/Mo(110) was
made in a similar way by dosing a phenol multilayer at 100 K followed by
a 600 K anneal. The preadsorbed oxygen serves to stabilize the phenoxide
species relative to the clean Mo(110) surface where it cannot be uniquely
isolated [10.67, 68].
The interpretation of the resonances in the phenoxide spectrum follows from
that of phenol discussed in Sect. 6.4.4 and shown in Fig. 6.29. Three n*
resonances and two 0"* resonances are observed. Note that the first 0"* resonance
contains both a C-C and C-O bond component. The splitting of the first two n *
peaks is 1.7 eV, which mostly reflects the difference in binding energy of the
carbon atom bonded to oxygen and of the rest of the carbon atoms in the phenyl
ring (Fig. 6.29). XPS measurements for phenoxide on O/Mo(llO) [10.67] give
these binding energies as 285.1 eV (C-O) and 283.6eV (C-C) with an intensity
ratio of 1 to 5. The corresponding splitting observed by XPS in phenyl thiolate
on Mo(llO) [10.69] is smaller, only 1.0eV, with binding energies 285.3 eV (C-S)
and 284.3 eV (C-C). Therefore the splitting between the first two n * resonances
is reduced in phenyl thiolate, and referring to Fig. 6.29 we have assigned the two
n* resonances observed in the normal incidence spectrum in Fig. 10.17a to
nearly degenerate resonances n! and n! on one hand and n; and n! on the
other, similar to benzene. The second resonance in the grazing incidence
spectrum is assigned to a C-S 0"* resonance [10.65] and its polarization
dependence indicates that the C-S bond is mostly perpendicular to the surface.
We also show in Fig. 10.17 the curve fits made in the original analysis [10.60,
 CS H SSH/Mo(110),200K CS HS OH/O/Mo(110),600K CS HS OH/O/Ag(110),500K

(a) 1tt2 (b) (e)

25°11~ 300l!'- 1'65 0

1t*
1 0..# p
"0 ~ V>
Q)
';-
1t2
, *
91 = "". +. ;;l
<1>
"",w'
* ~
o
c "1t~.4 ,: ~3
/«([),:c··~::. o
::I
'-
,,
...... 1t* &.
II ::I
Q) I1 Ot>
i:U i 2.,
II
ttl
1t*
;t1
't ., ,2 g
ttl .--.~ ~
a.. ~
s·
0;0
~
~1;~: __ L ... ~
(1)
~~~ vv*-, 0-
a:o
~
E.
i.l
,,_~!~~r~ o
280 290 300 310 320 280 290 300 310 320 280 290 300 310 320
Photon Energy (eV)
a:
<1>
§:.
V>
Fig. lO.17a--c. NEXAFS spectra of phenylthiolate (C6 H sS-) and phenoxide monolayer of atomic oxygen. A multilayer of phenol (C 6 H 6 0H) was adsorbed l:
'"1
(C 6 H sO-) on different surfaces. In all cases the X-ray incidence angles were 20° on 0 jMo(1lO) at 100 K followed by an anneal to 600 K [10.66]. (e) Phenoxide iii'
and 90°, respectively. The ring orientation determined by NEXAFS is shown on Ag(11O), precovered with one sixth of a monolayer of atomic oxygen. The ~
as an inset in each case. (a) Phenylthiolate on Mo(lIO), produced by dosing a surface was prepared by a multilayer dose onto the OjAg(lIO) surface at
multilayer ofbenzenethiol (C 6 H sSH) at 100 K, followed by an anneal to 200 K 100 K, followed by an anneal to 500 K [10.60] W
[10.64,65]. (b) Phenoxide on a Mo(11O) surface precovered with one third of a tv
W
324 10. Selected Applications of NEXAFS

65, 66], and the orientation of the rings determined from these fits. The absence
of any azimuthal dependence of the NEXAFS spectra of phenyl thiolate on
Mo(110) indicates that the ring plane is not preferentially tilted into a specific
azimuthal direction. This is probably due to the fact that the measurement
averages over domains which by themselves may have unique azimuthal order.
For phenyl thiolate on Mo(llO) the ring plane is tilted from the surface normal
by about 25° [10.65]. A similar analysis for phenoxide on O/Mo(llO) [10.66]
yielded a 30° tilt of the ring plane from the surface normal, again without any
azimuthal preference. The upright geometry of phenyl thiolate and phenoxide
is to be expected from the strength of the heteroatom-metal bond in organo-
metallic analogs (Table 6.1). For example, bond energies of 86kcal/mole and
111 kcaljmole have been calculated for the metal-sulfur and metal--oxygen
bonds in Ti(Cph(SC6Hsh and Ti(Cph(OC6Hsh. respectively [10.70]. These
bond energies are expected to be significantly larger than the n-bonding energy
with the surface.
The orientation of phenoxide on O/Mo(llO) is in marked contrast to that on
the 0/ Ag(llO) surface. The spectra shown in Fig. 10.17c were recorded for a
sample which was precovered with one sixth of a monolayer of atomic oxygen,
dosed with a multilayer of phenol and annealed to 500 K [10.60]. The presence
of preadsorbed oxygen activates the O-H bond, as observed for alcohols on
Ag(llO) [10.71], resulting in phenoxide and water formation. The phenoxide
intermediate is stable to temperatures in excess of 500 K with water desorbing at
lower temperature. The assignment of the resonances in the phenoxide on
0/ Ag(llO) spectra is identical to that for phenoxide on O/Mo(llO). The n*
resonances for the 0/ Ag(110) surface occur about 1 eV higher in photon energy
in agreement with the 1 eV larger XPS binding energies of 284.5 eV (C--C) and
286.1 eV (C-O) [10.60]. From the shown curve fits [10.60] in Fig. 10.17c the
phenyl ring is found to orient more parallel to the Ag(llO) surface, at a tilt angle
of about 65° relative to the surface normal, as illustrated in the figure.
The difference between the orientation of phenoxide on O/Mo(llO) and
O/Ag(llO) shown in Fig. 10.17b and c is most likely caused by different lateral
and/or molecule-surface interactions. While for Ag(110) the originally adsorbed
atomic oxygen is no longer present at 500 K (desorption as H 2 0), the presence of
chemisorbed 0 atoms in the case of Mo(llO) may inhibit a lying down
geometry. Also, a change in ring plane orientation may originate from a
difference in molecule-molecule interactions (see below). Unfortunately, we do
not know the phenoxide coverage in the two cases, but from the edge jumps it
appears that the coverage for phenoxide on Ag(llO) is lower, allowing the ring
to lie down. Finally, on Ag(llO) the bond of the oxygen heteroatom to the
surface may simply be weaker and comparable to the n-bonding interaction of
the ring.
Spectra similar to those shown in Fig. 10.17c are also obtained for sub-
monolayer phenol dosed onto the clean Ag(llO) surface at 100 K [10.60]. This
indicates that for both phenoxide and submonolayer phenol the n-bonding
interaction to the surface dominates. In contrast, on the clean surface a full
 10.5 The Bonding of Phenyl-Ring-Based Molecules to Metal Surfaces 325

monolayer of phenol was found to show only a 50° tilt of the ring plane from the
surface normal [10.60]. A more standing up geometry with increasing coverage
may in fact be a more general phenomenon for ring-like molecules. It is also
observed for benzene on Ag(llO) [10.60] and for pyridine on Ag(lll) [10.72] as
discussed below. This tilting-up of the ring plane from the surface can be
attributed to lateral interactions between the molecules. In particular, the
in-plane size of benzene, estimated from the van-der-Waals diameters of the
constituent atoms [10.73] is 34.2A2, while the cross-sectional area perpendic-
ular to the ring plane is only 22.3 A 2. Hence, the surface coverage can be
increased by tilting of the ring plane out of the surface plane.

10.5.4 Pyridine
The reaction and orientation of pyridine on metal surfaces is strongly influenced
by the lone pair orbital on the nitrogen atom. Thus one might expect a
competition between lone pair bonding producing a standing-up ring orienta-
tion or a lying-down species due to 11:* bonding. Indeed, pyridine on metal
surfaces shows some interesting orientational behavior, and we shall give
examples of NEXAFS determinations of bonding configurations of pyridine on
noble and transition metals below.
The first NEXAFS study of pyridine, by Johnson et al. [10.56], revealed the
different bonding behavior of pyridine and benzene. It compared the orientation
of benzene and pyridine monolayers on Pt(l11), prepared at room temperature.
Benzene was found to lie down and pyridine to stand up. The background-
corrected C K-shell spectra of pyridine on Pt(lll) obtained by Johnson et al.
[10.56] are shown in Fig. 10.18a compared to the spectra of gas phase and solid
pyridine [10.57]. The spectra look almost identical to those of benzene and, in
particular, the polarization dependence of the pyridine/Pt(l11) spectra readily
reveals the predominantly standing up orientation of the ring plane. We shall
come back to the bonding of pyridine on Pt(l11) after discussing an especially
interesting study of pyridine on Ag(lll) by Bader et al. [10.72].
What makes the NEXAFS work of Bader et al. special is not only that it
revealed an interesting coverage-dependent orientational transition, but also the
special way this study was carried out. Bader et al. studied the coverage-
dependent orientation of pyridine on Ag(111) by monitoring the 11:* resonance
intensity at the N K-edge. Although the adsorbate signal is smaller at the N K-
edge than at the C K-edge due to the fact that the ring contains only one N
atom, it offers the advantage of easier normalization. As discussed in Sect. 5.5,
the C K-edge region is typically plagued with pronounced structures in the
monochromator transmission function which need to be normalized out. Typi-
cal partial electron yield NEXAFS spectra recorded by Bader et al. are shown in
Fig. 1O.18b, peak A being the prominent 11:* resonance.
The intensity of this resonance (peak A) was monitored in a real time
NEXAFS experiment as a function of time under continuous adsorption of
pyridine on the crystal. This was accomplished by sweeping the photon energy
326 10. Selected Applications of NEXAFS

Ib) A C5H5N/Ag (111)

'0
Q;
N K-edge
>=
c:
e
'0
Q)
W
"iii
'1::
III
0..

390 400 410 420 430 440

Photon Energy (eV)
a
.o!a Ie)
,c.\

------- .....
o
N A'("\
,. , P
C c• 70·
g
.,
-
\
,..C> ..
M
p',C' 45· ~.c
.o
~ 2.2
IV'

---
,
'"
I II

>
'1;i 1.8 ?~
~ " A\, f ___
~ 3.4
~
.~
c:
E
--:-------=--
!!l1.4
-~------~-
3.0
.E 1.0 2.6 ~
«
.>< 0.6
III
•• : ~ f.
.-:. . .~ Multilayer
2.2.><
~ 0.2
• -1 Mono ayer
1.8 ~
2 3 4 5 6 7 8 15
Excitation Energy (eV) Dose (Langmuir)

Fig. lo.t8. (a) Carbon K-shell spectra of pyridine gas recorded by ISEELS, and NEXAFS spectra of
solid pyridine, condensed at lOOK on a Pt(111) surface, and a monolayer of pyridine dosed onto the
Pt(lll) surface at 300K [10.57]. (b) Nitrogen K-edge NEXAFS spectra ofa pyridine monolayer on
Ag(lll) at lOOK [10.72]. (c) Intensity ratio of the 71:* resonance [peak A in (b)], recorded at 20° and
90° X-ray incidence (triangles, left ordinate) and relative peak A intensity recorded at 90° incidence
(full circles, right ordinate) as a function of pyridine dose on Ag(lll) at 100 K [10.72]. The data were
taken continuously during dosing at a rate of ~ 0.1 Langmuir/min. There is a phase transition from
a 45° to a 70° inclined species, as indicated, near 4.5 Langmuir dose

at a rate of 30eV/min and continuously recording spectra while the chamber

was kept at a pyridine partial pressure of 1.6 x lO - 9 Torr, corresponding to a
dosing rate of 0.1 L/min [1 L (Langmuir) = lO-6 Torr s]. The peak A intensity
was then defined by subtracting from the intensity at a given time (exposure)
that of the clean crystal. The results are shown in Fig. 10.l8c both for the peak A
intensity ratio of grazing incidence versus normal incidence (120/190) spectra,
and the intensity of peak A recorded at normal incidence alone.
The measured intensity ratios 120/190 can be converted into tilt angles by use
of Fig. 9.5. Assuming no azimuthal orientation, this yields a tilt angle of the
plane relative to the surface of 45° at low coverage and 70° at high coverage, as
schematically shown in Fig. 10.18c. As discussed in the previous section for
phenol and benzene, this result can be explained by enhanced lateral inter-
actions between the pyridine molecule at higher coverage. The more upright
orientation of pyridine relative to benzene on the surface is the result of the N
lone pair donor bond contribution in pyridine, as indicated schematically in
Fig. 10.19a. With increasing coverage the importance of n-bonding to the
 10.5 The Bonding of Phenyl-Ring-Based Molecules to Metal Surfaces 327

(8) Tilted Pyridine (b) Upright a Pyridyl

<:::::CO
I
ceo
I
91°
Fig. 10.19. Change of orientation of pyridine on Pt(I11) from a 50 0 tilted low temperature state,
bonded via the N lone pair, to a high temperature near upright (70 0 tilt) IX pyridyl state, where the
surface bond involves both the N lone pair and a C-metal bond [10.74]

surface diminishes through stronger inter-molecular interactions. The domi-

nance of the N lone pair bonding at high coverage leads to a nearly upright
molecular orientation.
On the Pt(lll) surface a similar orientational change of pyridine occurs, in
this case as a function of temperature [10.74]. The origin of this transformation
is quite different. Johnson et al. [10.74] started with a multilayer of pyridine on
Pt(111) at 90 K and by annealing to 240 K created a monolayer. Analysis of the
1t * resonance intensity gave a 52° ± 6° tilt angle of the ring plane relative to the
surface. Annealing of the layer to 410 K resulted in a more upright pyridine
orientation of 74° ± 10°. A similar orientation, 85° ± 10°, was obtained for a
saturation dose of pyridine onto the surface at room temperature, followed by a
brief anneal to 320 K. The spectra for this latter case are shown at the bottom of
Fig. 1O.18a.
The origin of the observed orientation change is revealed by thermal
desorption data, showing the desorption of one hydrogen equivalent from the
Pt(I11) surface at 370 K. Since hydrogen itself also desorbs from the Pt(ll1)
surface near this temperature, it can be inferred that the C-H bond cleavage step
which creates hydrogen on the surface occurs at lower temperature, i.e., has
already occurred at 320 K, the lowest annealing temperature used by Johnson
et al. to create the upright pyridine species. This observation led the authors to
postulate the creation of an 0( pyridyl species above 320 K (Fig.l0.19b). This
species is attached to the surface via both a N lone pair and a carbon-metal
bond, with the plane of the ring perpendicular to the surface. Hence in this case
the driving force for an upright orientation is the formation of an additional
molecule-surface bond.

10.5.5 Reaction Intermediates: Benzyne

One of the more difficult problems in surface science is the characterization of
simultaneously present reaction intermediates. Hydrocarbon fragments are
especially difficult to distinguish owing to the wealth of possible and similar
conformations. Below we shall give a counterexample: the NEXAFS study of the
decomposition intermediates of benzene on Mo(llO) [10.58].
328 10. Selected Applications of NEXAFS

The spectra of chemisorbed benzene (C6H6) on Mo(llO), created by an-

nealing a multilayer to 200 K, have already been shown in Fig. 10.16. At this
temperature the ring is bonded to the surface in a lying down, n-bonding,
configuration. XPS spectra show a single C Is peak with a binding energy of
284:0 eV for this state which is stable between 200 K and 300 K. Thermal
desorption spectra reveal decomposition of benzene above 350 K through a
pronounced hydrogen desorption peak, and above this temperature the XPS
spectrum exhibits two peaks, centered at 283.9 eV and 282.9 eV, respectively
[10.58]. At 450 K, both peaks have roughly the same intensity, indicating the
presence of two reaction intermediates each containing half of the total number
of C atoms. Desorption data show further dehydrogenation occurring above
450 K, and by 700 K only the lower binding energy XPS peak at 282.9 eV
remains.
The NEXAFS spectra of C6H6 on Mo(llO) heated to 450 K, where the XPS
spectra indicate the presence of two reaction intermediates,. are shown at two
angles of X-ray incidence in Fig. 10.20a as a solid line [10.58]. Despite the
pronounced polarization dependence of the spectrum and the fine structure in

(a) Benzene (450K)

.......... (b) + (e)

(b) Benzene (700K) c C

...L.....L...

275 285 295 305 315 325275 285 295 305 315 325
Photon Energy (eV)

Fig. 10.20. NEXAFS spectra identifying several surface intermediates produced by benzene and
benzenethiol decomposition on Mo(llO) [10.58]. (a) Intermediates produced by annealing benzene
to 450 K. (b) Atomic carbon produced by annealing benzene to 700 K. (c) The benzyne (C 6 H 4 )
intermediate [10.64] produced by annealing benzenethiol (C 6 H sSH) to 600 K. The dashed curve in
(a) shows a best·fit addition of the benzyne [55% of (c)] and atomic carbon [45% of (b)] spectra.
Comparison of the synthesized spectrum to that recorded for benzene heated to 450 K identifies
benzyne and atomic carbon as simultaneously existing intermediates in the decomposition of
benzene on Mo(110)
 10.6 Thiophene on Pt(lll) and Poly thiophene on Pt 329

the 285-290eV region, the correlation of the spectrum with a particular molecu-
lar species is anything but straightforward. Figure 1O.20b shows the polar-
ization-dependent spectra of the same sample after annealing to 700 K, and this
spectrum is representative of atomic C on Mo(11O), since carbon is the only
element left on the surface after this treatment. The missing piece of the puzzle is
shown in Fig. 10.2Oc, where the spectrum of the benzyne (C 6 H 4) intermediate is
shown [10.64]. Benzyne was prepared by heating a multilayer of benzenethiol
on Mo(110) to 600 K [10.69J. Benzenethiol adsorption on Mo(110) first forms
benzenethiolate above 120K (Fig. 10. 17a), which around 350K undergoes
dehydrogenation and desulfurization to form atomic sulfur and benzyne
[10.69]. As indicated in Fig. 1O.20c, benzyne stands up on the surface.
The spectra of the benzene decomposition products in Fig. 10.20a can be
accounted for by a superposition of the respective spectra for atomic C
(Fig. 10.20b) and the benzyne spectra (Fig. 1O.20c). The dotted lines in
Fig. 1O.20a show the composite spectra obtained by least-squares fitting of
variable fractions of the respective spectra (b) for atomic carbon and the spectra
(c) for benzyne. At both angles of incidence the fits yielded an optimum
composition of 45% of (b) and 55% of (c). This relative contribution is in good
accord with the approximately equal XPS peak intensities for the two carbon
species. Icons on the right side of Fig. 10.20 summarize the surface species
corresponding to the various spectra. The temperature-induced change of the
ring orientation from parallel to the surface for benzene (below 300 K) to
perpendicular to the surface for benzyne ( ~ 450 K) bear a certain resemblance to
the change from pyridine to ex pyridyl on Pt(111). Both transformations are
driven by cleavage of C-H bonds and their substitution by carbon-metal bonds.
The above example also demonstrates yet another use of NEXAFS, which
may be called the fingerprint method. Without understanding in detail the origin
of the structures in the NEXAFS spectrum of a certain surface species, one may
simply identify the spectral "fingerprint" with the species, as was done for the
atomic carbon spectrum in Fig. 1O.20b. This "fingerprint" can then be used for
recognition of the surface species, even in complex situations as in Fig. 10.20a.
The fingerprint method has already been mentioned in Sect. 6.5 in conjunction
with macromolecules and it has also been successfully applied in the interpreta-
tion of near edge spectra of surface compounds [1O.75J, geological samples
[10.76, 77] and trace elements [10.78].

10.6 Thiophene on Pt(I11) and Polythiophene on Pt

Thiophene, C 4H 4S, is an interesting and important molecule. It is a five-

membered heterocyclic ring, like pyrrole (C 4 H4NH) and furan (C 4H 40). The
molecule is aromatic, with the two C-C "double bonds" of 1.37 Alength and the
1.42 A long "single bond" being rather similar due to strong conjugation. In
catalysis-related surface science studies, thiophene is used as a model for sulfur
330 10. Selected Applications of NEXAFS

bonding in oil, coal, and pertroleum [10.79], and its interaction with transition
metals and transition-metal sulfides has long served as a model for the in-
dustrially important hydrodesulfurization (HDS) process [10.80]. In HDS the
goal is to extract sulfur from the surrounding hydrocarbon skeleton in fuel
feedstock by a suitable catalyst. This is necessary because the sulfur would
poison other catalysts used later for reforming the hydrocarbon skeleton into
high-octane gasoline. Low sulfur content in gasoline also minimizes production
of environmentally deleterious sulfur oxides in combustion and reduces deacti-
vation of "catalytic converters" in automobiles. The key step of the HDS
process, namely the C-S bond cleavage, is still not understood well. As the name
implies, HDS has typically been thought to involve hydrogenolysis, i.e., substitu-
tion of hydrogens for sulfur, to satisfy the overall valency requirements after ring
opening.
A second area where thiophene is of importance is polymer science. Organic
conducting polymers, such as polyacetylene, polypyrrole or poly thiophene, have
been the subject of much study because their electrical conductivities can be
varied over 12 orders of magnitude by chemical or electrochemical doping
[10.81]. Such polymers have potential applications in a wide variety of devices,
such as displays, organic batteries, or solar cells [10.82]. Poly thiophene and its
derivatives are particularly attractive because of their high chemical and electro-
chemical stability [10.83].
In this section we will show the power of NEXAFS in providing information
on the bonding and transformation of thiophene molecules on Pt(111), first
studied by Stohr et al. [10.84], and the bonding and orientation of poly-3-
methylthiophene, electrochemically deposited as a monolayer on a Pt electrode,
studied by Tourillon et al. [10.85]. A remarkably similar picture of the orienta-
tion of the thiophene rings relative to the surface will emerge. We begin with the
study of the bonding and desulfurization of the thiophene molecule on Pt(111).
NEXAFS spectra above the sulfur L 2 ,3 and the carbon K-edge for thiophene
on Pt(lll) are shown in Fig. 10.21 [10.84]. The molecules were deposited by
dosing the clean Pt surface, kept at 90 K, with a multilayer of thiophene, and
then heating the crystal momentarily to the temperatures indicated in the figure.
The S L2,3-edge at 180K, corresponding to monolayer coverage, exhibits two
pronounced structures, X and Y, around 166 and 174eV. Xcx-MS calculations
[10.87] reveal that peak X corresponds to transitions of S 2p electrons to closely
spaced unfilled n * and (j * molecular orbitals associated with the S- C bond in
thiophene. Polarization-dependent spectra [10.87] indicate that in the glancing
X-ray incidence spectra shown in Fig. 10.21a peak X is primarily associated with
transitions from the 2Pl/2 spin-orbit component, which lies about 1.2 eV higher
in energy than transitions from the 2P3/2 component, the latter dominating at
normal X-ray incidence. Peak Y is associated with a substrate-enhanced atomic
resonance in the continuum [IP(2p3/2) = [Link] and IP(2pl/2) = 171.1 eV in
the gas phase] due to transitions to d-like (t 2g ) final states. A similar feature is
seen in most S L-edge spectra [10.88]. With increasing temperature peak X
decreases in intensity and has vanished at 470 K, while peak Y shows the
 10.6 Thiophene on Pt(I11) and Polythiophene on Pt 331

Experiment Xa-MS Theory

S L-edge C K-edge C K-edge

f:: j./'
lal Ibl leI

Q) AB C D

] ::: I I 1

2.0
1/
, I
160 170 180 280 290 300 310 320 10 20
Photon Energy leV) Energy from IP leV)

Fig. 10.21. (a) NEXAFS spectra recorded at grazing X-ray incidence for the S L 2 • 3 -edge for C 4 H 4 S
on Pt(111) after annealing to different temperatures [10.84]. Peak X represents a resonance
characteristic of the C-S bond. (b) Spectra recorded at normal X-ray incidence for the C K-edge
under the same sample conditions as in (a). Note the disappearance of resonance B associated with
the C-S bond. (c) XIX-MS calculation [10.86] of the C K-edge cross section for the free thiophene
molecule (top) and a metallacycle where the S atom has been replaced by a Pt atom (bottom). In both
cases the electric field vector was assumed to be in the plane of the molecule, and its orientation was
azimuthally averaged. The spectra are plotted as a function of excitation energy relative to the IP,
which for the free molecule is 290.3 eV [10.87]

opposite behavior. A similar temperature dependence is also observed at normal

X-ray incidence [10.87]. The vanishing intensity of peak X with increasing
temperature unambiguously indicates the cleavage of the S-C bond in the
molecule. We therefore observe that on the Pt(111) surface S-C bond breaking
has already begun at 290 K and is completed at 470 K. The increase of peak Y
with temperature is related to a redistribution of oscillator strength into another
channel, according to the f-sum rule (Sect. 2.1.2).
NEXAFS spectra above the C K -edge in the same temperature range
(Fig. 10.21b) support the above conclusions. Four resonances A-D, can be
discerned. In the unperturbed molecule, resonance A is associated with trans-
itions to n*orbitals, arising from the C=C "double bond" in thiophene. Reson-
ance B arises predominantly from excitations to antibonding (1* orbitals associ-
ated with the C-S bond, and resonances C and Dare (1* resonances associated
with C-C bonds. In particular, the C-S (1* resonance, peak B, follows the
intensity change of peak X in Fig. 1O.21a. The evident cleavage of the C-S bond
is accompanied by an increase of the intensity of peak A. This was interpreted by
Stohr et al. [10.84] as· the formation of C-Pt bonds, with peak A arising from
transitions to newly formed (C-Pt)* orbitals as discussed in Sect. 10.4. Note that
the C-Pt resonance occurs at a slightly (0.5 eV) lower energy than the C=C n*
resonance in the unperturbed molecule and also at the opposite X-ray polariza-
 332 10. Selected Applications of NEXAFS

tion (see below). Based on the above considerations and on the similarity of the
C-C resonance structures, Stohr et al. proposed the formation of a Pt cyclopen-
tadiene metallacycle [10.89] upon desulfurization where the C-S bond is simply
replaced by a C-Pt bond.
In order to determine the orientation of thiophene and the created metalla-
cycle with respect to the surface, we need to consider the polarization depend-
ence of the C K-edge NEXAFS spectra. This is shown for the thiophene
monolayer at 180 K in Fig. 10.22a. In fact, the normal incidence spectrum shown
in this figure is the same spectrum as shown at the top of Fig. 10.21b, but it has
been background-corrected and smoothed [10.87]. The polarization depend-
ence unambiguously shows that, at monolayer coverage, the thiophene molecule
lies flat on the surface, since all u* resonances are largest at normal incidence,
and the 11: * resonance dominates at grazing incidence. Since the two C-C
resonances C and D in the bottom spectrum in Fig. 10.21b are still strong and
the spectrum was taken at normal X-ray incidence, the metallacycle must also be
oriented with its plane close to the Pt surface. This geometry would predict that
the Pt metallacycle maintains additional 11: bonding to the surface. Such a
bonding arrangement shown in Fig. 10.23a is similar to that reported for an
organometallic complex formed by the interaction of thiophene and Fe car-
bonyls [10.90], shown in Fig. 10.23b.
The original spectral assignments and conclusions [10.84] are supported by
subsequent XIX-MS calculations by Horsley [10.86] for the C K-shell, shown in

la)
It,' Q Ib)
It,'
I I

E E
'2
'2
.e.!!a .e.!!a
:J :J

"0 "0
a; a;
>= >=
c c
g e
0 '0
'"
iii '"
iii
iii Q;
"f Cl
8!. «
:J

Photon Energy (eV)

Fig. 10.22. (a) Polarization-dependent NEXAFS spectra for a monolayer of C4 H4 S on Pt(ll1),

produced by a multilayer dose at 90 K followed by heating the crystal briefly to 180 K. The spectra
are taken from [10.87]. (b) Spectra of a monolayer of poly-3-methylthiophene, electrochemically
grafted on Pt [10.85], as a function of X-ray incidence
 10.7 Langmuir-Blodgett Chains on Si(111) 333

co
" /~
CO~Fe- ::
~~ :
~ Fe
Cu / A"-
(b) CO CO '~CO

Fig. 10.23. (a) Proposed geometry of the C4 H 4 Pt metallacycIe formed by desulfurization of C4 H 4 S

on Pt(lll) [10.84]. (b) Organometallic complex C4 H4 Fe 2 (CO)6, formed by co-condensation of iron
vapor and thiophene at -196°C, followed by a warm up in a CO atmosphere [10.90]

Fig. 10.21c. The calculations were carried out for gas phase thiophene (top) and
a Pt metallacycle (bottom), in both cases assuming that the E vector was in the
molecular plane (azimuthal average). In beautiful agreement with experiment,
i.e., the top and bottom curves in Fig. 10.21b, the calculation predicts the near
disappearance of resonance B and the appearance of resonance A upon metal-
lacycle form-ation. The weak left-over resonance B in the metallacycle spectrum
is due to a second C-Pt resonance [10.86].
The above study is an example of the power of NEXAFS to reveal and
characterize important catalytic processes. Since the original study [10.84] was
based on the interpretation of NEXAFS spectra simply by application of
empirically derived rules, it also emphasizes the ease of interpretation of
NEXAFS spectra. With respect to the HDS process, it showed for the first time
that cleavage of the C-S bond may occur without the presence of atomic or
molecular hydrogen, and that desulfurization is readily possible below room
temperature on transition metal surfaces. The observed metallacycle species is
believed to be an intermediate in the desulfurization process, undergoing
decomposition to butadiene at higher temperatures. Butadiene desorption is
indeed observed from Pt(1l1) [10.91]. Similar desulfurization effects were later
found for thiophene on Ni(I00) [10.92] and other sulfur containing molecules
on other metal surfaces [10.64, 93].
Finally, the NEXAFS spectra for a monolayer of poly-3-methylthiophene,
electrochemically grafted on Pt [10.85], shown in Fig. 10.22b, show a remark-
able resemblance to those for thiophene on Pt(1l1), shown in Fig. 1O.22a. The
rings in the polymeric layer are thus n-bonded to the surface, just like the
individual thiophene molecules on Pt(III). These results and those discussed in
Sect. 6.5 indicate the power of NEXAFS for the study of thin polymer films.

10.7 Langmuir-Blodgett Chains on Si(U1)

Saturated hydrocarbon chains, (-CH r -CH 2-)n, are important components of

many polymers, the best known being polyethylene, which consists exclusively
of such chains. Hydrocarbon chains (mostly saturated) with a carboxyl
334 to. Selected Applications of NEXAFS

(-COOH) terminus are called fatty acids. In nature fatty acids are build-
ing blocks of lipids which in turn are important components of membranes
[10.94, 95]. In technology fatty acids attached to a substrate surface via the
carboxyl group may serve as thin lubricant films. This section deals with such
systems, which are typically prepared by the Langmuir-Blodgett (LB) technique
[10.96, 97].
The LB method allows the formation of well-defined monomolecular layers,
each on the order of 30 A thick. Typically these films consist of fatty acids
CH3(CH2)nCOOH (~C12) or the salt with a -COO- end group. Under
appropriate conditions (pH and temperature) a monolayer or multilayer LB film
can be transferred to a solid surface by successive dipping of a substrate through
a compressed layer of molecules on a water surface. LB films are highly ordered
with parallel hydrocarbon chains as in the crystalline fatty acids [10.98].
Numerous applications of these films have been discussed [10.99], including use
in microlithography, electro optics, bio-chemical sensing and tribology. Essen-
tial for system design, however, is a detailed characterization of the molecular
structure of the film. A range of techniques have been adapted for this purpose,
from the early optical measurements of the indices of refraction and interference
patterns [10.96] to more recent infrared [10.100] and Raman [10.101] spectro-
scopies, angle-resolved photoemission [10.102], electron, [10.103] and X-ray
[10.104, 105] diffraction, and scanning tunnelling microscopy [10.106].
The structural behaviour of long chain molecules has also been investigated
theoretically by molecular dynamics calculations [10.107]. NEXAFS measure-
ments on monolayers of cadmium (CdA) and calcium (CaA) arachidate
(M[CH 3 (CH 2ltsCOO]2)' where M = Cd or Ca, on a Si(l11) wafer were
first carried out in 1987 by Outka et al. [10.108-110], and in the following we
shall review their results.

10.7.1 Experimental Results

Figure 10.24 compares the angular dependence of the NEXAFS spectra of CdA
and CaA films [10.108]. The top row shows the spectra at normal and the
second row at glancing X-ray incidence. The spectra are scaled to the same edge
jump by matching their intensities at 275 eV and 320 eV. The bottom row shows
the results of subtracting the glancing from the normal incidence spectra,
respectively. This clearly isolates three angle-dependent resonances, A-C, of
which resonance A has the opposite angular dependence to resonances Band C.
Also, CdA is seen to exhibit a greater angular dependence than CaA. As
discussed in Sect. 6.4.3, resonance "A" is associated with C-H orbitals, and
resonances "B" and "c" are associated with the C-C antibonding orbitals, split
by bQnd-bond interaction effects. The CdA spectra were previously shown in
Fig. 6.20, in comparison to those of polyethylene.
In order to accurately determine the orientation of the chains on the surface
a series of NEXAFS spectra of the LB films were measured as a function of E
vector orientation relative to the surface normal in 10° intervals from 20° to 90°.
 10.7 Langmuir-Blodgett Ch,,1110 on Si (Ill) 335

Cd Arachldate Ca Arachldate Fig. 10.24. Comparison of the angular

dependence of the NEXAFS spectra of
films of Cd arachidate and Ca arachidate
....
-
C
::J
20

10
on a Si(l!l) surface. The top row shows
the spectra at normal X-ray incidence
(90°), the second row at glancing inci-
...
.Q dence angle (20°), and the bottom row
-< 0 shows the result of subtracting the glan-

-•
........
>- cing incidence spectra from the normal

-
' ii 20 incidence spectra. This reveals three an-
c::
gle-dependent resonances A, B, and C.
.E 10 Note the stronger angular dependence of
the Cd arachidate spectra
0
u• 10

-
c::
•
... 5
• 0
0 -5
-10 A
280 300 320 280 300 320
Photon Energy (eV)

~~
8=90° 8=90°

0-
aL!)
(a) II (b) 1/\
-;;; ~

,,=
c ..,> ~
:J 'r:;;
C i?,I
of:ctJ 8=20° ..,
Q)
~
C
1\1
..,>
'r:;;
c ~

.., ..,> ~B
Q)

c 'r:;;
c
B C
..,
Q)

c
8=20°
A
A

280 290 300 310 320 280 290 300 310 320
Photon Energy (eV)

Fig. 10.25. (a) Carbon K-edge NEXAFS spectra of a Cd arachidate film on Si(lll) at X-ray
incidence angles ranging from 90° to 20 in 10° increments. The resonances are labelled as in
0

Fig. 10.24. (b) Difference spectra obtained by subtracting the spectrum recorded at a 50° incidence
angle in (a) from each of the spectra at the other angles of incidence in (a). This series of difference
spectra clearly identifies the angular dependence of peaks A, Band C
336 10. Selected Applications of NEXAFS

The spectra shown in Fig. 10.2Sa, which were normalized to the same values at
27SeVand 320eV, clearly show the pronounced angular dependence of the
three principal resonances A-C. It is also apparent that there are sizable
isotropic structures in the background which must be separated from the
angular dependent structure in order to interpret the results quantitatively.
These isotropic components of the NEXAFS spectra, whose origin will be
discussed later, are removed in the "difference spectra" shown in Fig. 10.2Sb. In
particular, we have plotted the difference between a given spectrum recorded at
an X-ray incidence angle () (corresponding to an angle () between E and the
surface normal) and the spectrum recorded at a reference angle () = SO°, i.e.,
close to the "magic angle". This procedure isolates three clearly defined angle-
dependent resonances A-C, which can now be studied in more detail.
The curve fitting of resonances A-C has already been discussed in Sect. 7.2.2,
and an example was shown in Fig. 7.3. Peaks A and B were fitted with
symmetric Gaussians and peak C with an asymmetric Gaussian. The areas
obtained from fits of the difference spectra in Fig. 1O.2Sb are plotted as filled

Cd Arachidate
10

llllU
0
0
0
LD -10
II
~
20
~

iZT
·iii Ca Arachidate
c 10
.'!l
c 0

§ -10

~
-20
·iii
c
.'!l 10
c

-10

0 20 40 60 80
X-Ray Incidence Angle, e (degl
Fig. 10.26. (a) Intensities 1(0)-1(50°) of peaks A, D, and C in the difference spectra shown in
Fig. 1O.25b as a function of the X-ray incidence angle O. For all three peaks, the angular dependence
is greater for Cd arachidate than for Ca arachidate. Also shown are fits of the data points according
to (9.24) with the geometry factors 9 given by (10.1) and (10.3) for the C-C and C-H resonances,
respectively. (b) Proposed models for the hydrocarbon chain orientation in films of CdA and CaA.
The CdA chains are normal to the surface, while the CaA chains are tilted by 33°. In (c) it is shown
how the efficient packing of the chains with periodicity R depends upon the tilt angIe"t and minimum
separation D between chains
 10.7 Langmuir-Blodgett Chains on Si(l11) 337

circles and triangles in Fig. 10.26a versus the X-ray incidence angle (). The lines
through the data points are theoretical fits.

10.7.2 Chain Tilt, Intra-Chain Bonding, and Origin of Resonances

The theoretical expressions describing the angular dependence of resonances
A-C depend on the way the chains are tilted and the molecular orbital picture of
the intra-chain bonding. Below we shall follow the approach used by Dutka et al.
[10.109]. Although this model has been challenged by H iihner et al. [10.111], we
have chosen it here because of its simplicity and transparency. Also, the
mathematical expressions for the angular dependence of the resonance in-
tensities in this model are readily adapted to other models.
Dutka et al. [10.109] proposed a "tilted-chain" model for the LB chains on
silicon. Each individual hydrocarbon chain in this model is assumed to tilt only
in the plane containing the C-C-C bonds and to have an all trans geometry. In
different domains chains are tilted by the same angle but may be tilted in
different directions. For a substrate with threefold symmetry an average over
different domains leads to the disappearance of any azimuthal dependence. This
is treated mathematically by integration over the azimuthal angle (Sect. 9.4.3).
The C-C bonds are treated as isolated vector-type orbitals where each
hydrocarbon chain has two C-C bonds with C-C-C bond angles of about 115°.
For example, for a vertical chain orientation, both C-C bonds make an angle of
32.5° with the surface normal. Each carbon atom in the chain is bonded to two
hydrogen atoms as shown in Fig. 6.20. In our analysis we will treat these two
bonds as vector orbitals, with an included H-C-H angle of 110°, and also
average over domains, i.e., azimuthal angles.

10.7.3 Analysis of Difference Spectra

While the orientation of a chain on a given sample cannot be deduced from its
difference spectra (Sect. 9.8), the difference spectra of two similar systems may be
compared, however, to obtain their relative orientation. For example, since Cd
and Ca arachidate are so similar and since the same detection apparatus was
used in both measurements, the constant C in (9.24) for these molecules can be
assumed to be the same. Let us for the following discussion abbreviate the
geometry factor gv(cx) in (9.24) simply by gCd for CdA and gCa for CaA. Then if
the scale factor SCd = CgCd is divided by SCa, the constant C cancels out,
and an expression relating the geometries of the two molecules is obtained:
R = SCa/SCd = gCa/gCd. The ratios R derived by fitting the experimental data to
(9.24) as shown in Fig.1O.26a are: R = 0.710 for the C-H* resonance (peak A),
R = 0.652 for the first C-C a * resonance (peak B), and R = 0.656 for the second
C-C a* resonance (peak C).
The values for the two C-C a* resonances are quite similar, indicating that
the angular dependence for these resonances is the same. This supports our
earlier assignment of resonance "c" in Sect. 6.4.3 as related to the C-C bonding.
338 10. Selected Applications of NEXAFS

The ratio R for the C-H * resonance, however, is significantly different. This is
because the C-H orbitals make a different angle with the surface normal than
the C-C orbitals. In order to interpret these R values in terms of relative
geometries of the two LB films, we need to derive a more explicit expression for
the geometry factor g in terms of the microscopic chain parameters and the
macroscopic tilt angle t of the chain with respect to the surface normal.
For the C-C bonds, the contributions of the two local C-C bond vectors
described by (9.24) are added together. This is done by expressing the geometry
factors g(oc 1) = 1 - (3/2) sin 2 oc1 and g(OC2) = 1 - (3/2)sin 2 oc2' where OC 1 and OC2
are the angles of the two C-C bond vectors relative to the surface normal, in
terms of the macroscopic tilt angle t and the C-C-C bond angle (jccc. We obtain

(10.1)

The average ratio, gg;c /ggi c = 0.654 measured for the two C-C (]"* resonances
implies that the Ca arachidate hydrocarbon chain is tilted significantly more
than the Cd arachidate chain. Assuming that the hydrocarbon chain of Cd
arachidate is oriented normal to the surface and that (jccc = 115 we find that
0
,

the hydrocarbon chain of Ca arachidate is tilted by t = 33.8 0 •

Because the geometry of the C-H and C-C bonds differs, the C-H*
resonance gives an independent measure of the relative tilting the Ca and Cd
arachidate chains. The starting point for describing the C-H orbitals is again
(9.24). In the limiting case of hydrocarbon chains being normal to the surface,
the C-H bonds are parallel to the surface, t = 0 and OCC-H = 90 As the chain
0
,
0
•

tilts OCC-H decreases. Using the same tilted-chain geometry as above, the relation-
ship between the tilt of the hydrocarbon chain, t, and OCC- H (the angle the C-H
bonds make with the surface normal) is

sint )
OCC-H(t) = arccos ( (j, (10.2)
1 + tan 2 HCH
2

where (jHCH is the H-C-H bond angle. This leads to a geometry factor

gC-H(t) = 1 - i(1- cos2t + cos (jHCH - cos 2t cos (jHCH) . (10.3)

With (jHCH = 110 and the experimental observation that gg;H/ggi H = 0.710 we
0

obtain a tilt of t = 32.8° for Ca arachidate assuming the Cd arachidate chain is

normal to the surface (t = 0 This differs by only a degree from the 33.8 0 value
0
).

obtained from the C-C (]"* resonances, so the data from the C-H and C-C
resonances are remarkably consistent.

10.7.4 Curve Fits of Original Spectra

From the difference spectra only the orientation of a molecule relative to a
similar molecule can be obtained. In order to determine the absolute orienta-
 10.7 Langmuir-Blodgett Chains on Si(lll) 339

tions of either Ca or Cd arachidate one must analyze the original spectra. These
are composed of several features, some of which depend upon angle and some of
which do not. The angle-dependent features have already been identified from
the difference spectra. The isotropic features, on the other hand, which are
significant as revealed by inspection of Fig. 1O.25a, drop out in the difference
spectra. We can try to identify the isotropic peaks by curve fitting, as done in
Fig. lO.27a for the normal incidence CdA spectrum. Here we have generated an
angle-dependent NEXAFS spectrum (shown as a dotted curve) by superposition
of angle-dependent Gaussian lineshape functions obtained previously from fits
of peaks A-C in the difference spectra (shown dashed) and an appropriate step
function (also shown dashed), taken to be an error function (7.8). For the step
function a linearly decaying background was also added to represent the decay
which is normally observed in X-ray adsorption spectra above the edge. It was
established by a fit to the flattest region above the step which occurs between

....

+1
E

(c) • Resonance A
B .. Resonance B
1.2 .. Reso~eC
I:
I: -- Tilt= C1'
iii I: .............. Tilt = 10°
.t:: I:

E
.: ----- Tilt = 20°
c
::I

...co
.ri ~~.~ -'i.•.".:.:.:.~.~.•.•.• c
::I
.-.- Tilt = 3C1'

• .ri
....> """ Iii 0.8
'wc ""
II
II ....>
....c
CI)
I
II ,"
'wc
(a) ,
:,' \ ~
'I '~"'==:"':I c
• Constant Background 0.4
l'
: \ l~'·\.
(b) : I ' '-..,
..........."--.:.:
':""\! '. , _-.. - ....................... ..
...

280 290 300 310 320 o 20 40 60 80

Photon Energy (eV) X-Ray Incidence Angle, () (deg)
Fig. 10.27. (a) The original spectrum for Cd arachidate at normal X-ray incidence (solid line) is
composed of three angle-dependent peaks and an absorption step (individual features are dashed
and the sum is dotted) and an isotropic background [shown in (b)]. The size of resonance B, the C-C
u* resonance, shown here is just large enough to be consistent with a hydrocarbon chain orientation
normal to the surface. (b) Isotropic background determined by subtracting the dotted curve in (a)
from the data. (c) Plots of the areas of resonances A, B, and C obtained from fits of the original Cd
arachidate spectra after subtracting the isotropic background of (b) from each spectrum. Also shown
are curve fits of the data according to (9.23) as a function ofthe macroscopic tilt angle 7:, which can be
expressed in terms of the orbital tilt angle a: as discussed in the text. We have assumed a polarization
factor P = 0.85
340 10. Selected Applications of NEXAFS

315 eV to 325 eV in the glancing incidence spectra. The isotropic background is

then identified by taking the difference between the original spectra and the
synthesized angle-dependent spectra, e.g., the dotted line spectrum in
Fig. 10.27a. The result for the so-determined background of the normal in-
cidence CdA spectrum is shown in Fig. 10.27b. This background was found to
be identical for spectra taken at other incidence angles.
In the final analysis of the original spectra, the "constant background" plus
the isotropic step function was subtracted from each of the spectra. The resulting
spectra were least-squares fitted to Gaussian (peaks A and B) and asymmetric
(peak C) Gaussian peaks whose shapes were determined by the difference
spectra, with the intensities being the only free parameters. The resultant
intensity variation of the three angle-dependent peaks are shown in Fig. 10.27c.
Here the intensities of the peaks A-C are plotted as a function of the orientation
of the E vector relative to the surface normal. Also shown is the intensity of these
peaks, calculated according to (9.23) as a function of tilt angles 0° ~ 't' ~ 30° of
the hydrocarbon chain. The calculated intensities of the C-C u* resonances
were obtained by summing the results for the two C-C bond vectors and
expressing the two angles !Xl and!X2 in terms of the angles <5 ccc and 't' as for (10.1).
For the C-H* resonances, (9.23) in combination with (10.2) was used. In both
cases we assumed a polarization factor P = 0.85. The fit in Fig. 10.27a shows
that at normal incidence the intensity of peak B is not zero, as one would expect
from visual inspection of Fig. 10.24 or Fig. 10.25a, but that its intensity is hidden
by the adjacent large peaks in the constant background. From the analysis given
in Fig. 10.27c we conclude that the CdA chains are oriented normal to the
surface with an uncertainty of ± 15°.
The "constant background" identified in Fig. 1O.27b has probably several
contributions. Part of the peak stretching from 295 to 305 eV is certainly due to
the carboxylate group of the arachidate. In particular, resonances of the C-O
and C=O u* bonds are expected in this region from comparison to the spectrum
offormic acid (see Fig. 8.24), which has such features at 296.5 eV and 303.5 eV.
Resonance structures near 290eV may be associated with a C=O 1[* resonance.
The carboxylate group contributes only one out of twenty of the carbon atoms
of the arachidic acid molecule, however, so the overall intensity of these features
is expected to be relatively small. Since the LB films were prepared in air there is
most likely some contamination of carbon or organics adsorbed on the silicon
surface or on top of the LB layer, which would also contribute to this constant
background.

10.7.5 Structural Results

There is a simple geometric argument which can account for the stability of the
two orientations, 't' = 0° and 't' = 33°, found for CdA and CaA, respectively, as
shown in Fig. 10.26b. Adjacent hydrocarbon chains can interlock "in phase" at
certain tilt angles. This arises from the rather strong van der Waals interaction
between the close-packed chains as in fatty acid crystals [10.98]. This condition
 10.7 Langmuir-Blodgett Chains on Si(111) 341

is fulfilled for an upright chain orientation on the surface, and again, when the
chain has tilted to allow slippage of adjacent chains by multiples of the chain
period R. Figure 10.26c shows that this is satisfied when

nR
tan r = D' n = 0, 1,2, ... , (10.4)

where r is the tilt of the hydrocarbon chain from the surface normal, R is the
periodicity of the chain, i.e., the distance between second nearest-neighbor
carbon atoms (R = 2.52 A), and D is the minimum separation between hydro-
carbon chains. If the chains are vertical (r = 0° and n = 0), (10.4) is satisfied for
any separation D. If the chains are tilted, however, then crowding between the
chains becomes important and only certain angles are allowed. For example, the
minimum separation typically allowed between carbon atoms in adjacent
organic molecules is D = 3.6 to 4.0 A[10.112]. This yields a tilt angle of 32° to
35° using (10.4), which is in excellent agreement with the 33° ± 5° tilt angle
determined for Ca arachidate. Thus Cd and Ca arachidate satisfy (10.4) with
values of n = 0 and 1, respectively.
Figure 10.26b suggests that CdA with its vertical chain is bonded to the
surface with only one oxygen atom, while CaA with its tilted chain is almost
perfectly chelated with both oxygens on the surface. The bidentate surface bond
may additionally stabilize the 33° tilted configuration observed for CaA. It is not
clear, however, what role the cation plays in the surface bond. Both cations are
in + 2 oxidation states and are approximately the same size as estimated from
the metal-oxygen nearest-neighbor distances in crystalline CaO and CdO,
which are 2.405 Aand 2.347 A, respectively [10.113]. It is possible that the main
reason for the different orientations lies in the conditions during the transfer of
the films, e.g., the pH of the solutions. Whatever the reason, our results establish
that certain molecular orientations on the surface are favored by the in-phase
interlocking of adjacent chains. More generally, the present study demonstrates
the power of the NEXAFS technique to investigate the orientation and structure
of thin organic films on surfaces.
The results of this NEXAFS study are in general agreement with previous
studies regarding the orientation of LB films. For example, previous studies of
the orientation of Cd arachidate multilayers on silver and silver bromide
substrates found that the hydrocarbon chains were oriented nearly normal to
those surfaces, just like on the Si(111) surface of this study [10.100]. Also, on
glass waveguides a perpendicular orientation of the hydrocarbon chains was
found [10.101]. Indeed, it seems as if these are not epitaxial films since the
orientation is considered to be independent of the substrate [10.114].
11. A Look into the Future

With the availability of dedicated (second generation) synchrotron radiation

sources around the world and suitable soft X-ray monochromators, such as the
SX-700 plane grating [11.1, 2] or Dragon spherical grating [11.3, 4] instru-
ments, conventional NEXAFS studies in the 1990s are limited neither by flux
nor by resolution. Although many improvements in instrumentation are poss-
ible, to conclude this book we want to ask whether there are any truly novel and
exciting opportunities on the horizon. In the following let us therefore do some
brainstorming about possible future applications ofNEXAFS spectroscopy. We
shall restrict ourselves to novel ideas not mentioned in previous chapters. Most
of these ideas are centered around new instrumentation in the form of new
synchrotron radiation sources, novel monochromators or simply end-of-line
equipment.

11.1 Micro-NEXAFS

Third generation synchrotron radiation sources [11.5, 6] are centered around

insertion devices, most notably undulators. Undulator sources on planned rings
will provide only slightly more flux (factor ~ 5) than insertion device sources on
existing rings and in this respect offer little advantage. They will, however,
provide orders of magnitude higher brightness, defined as the ratio of flux and
emittance. The emittance of a source, defined as the product of source size al1d
solid emission angle, is a true measure of its quality since it is a conserved
quantity. It can never be improved by X-ray optics, only spoiled. The reduced
emittance of third generation rings allows one to design optical systems that
accept nearly all of the photon flux from the source and condense it without
significant loss into a small spot (down to a few hundred angstroms) on the
sample [11.5]. This capability is the cornerstone of a new approach called
spectromicroscopy, where high-resolution spectroscopic information is
obtained at high spatial resolution. Developments in this field have recently
been reviewed by Tonner [11. 7].
For NEXAFS spectroscopy it is necessary that the photon energy be easily
scannable while a microscopic area of the sample is examined. This is best
accomplished by forming a spot of moderate size on the sample, approximately
111m2, and using magnetic [11.8] and/or electrostatic [11.9] electron optics to
 11.2 Liquid Surfaces 343

form an enlarged image of the illuminated area on a video screen. In this scheme
the incident X-ray beam is thus focused to obtain a high flux density in the field
of view of the electron optics and the spatial resolution is set by the electron
optics. Attractive features of this approach are video-like data rates and zoom
capabilities. Spatial resolution in the 100 Arange appears to be a realistic goal.
By use of such instruments it will be possible to generate elemental micro-
scopic maps of surfaces by subtracting images obtained above and below
absorption edges [11.8, 9]. In addition, even for the same element one can
discriminate between different chemical forms in different areas of the sample by
recording complete NEXAFS spectra. For example, one may readily detect
graphitic areas on the surface of a diamond film made by chemical vapor
deposition because of the prominent n* resonance associated with Sp2 hybri-
dized carbon (Fig. 6.30). Other applications lie in the inspection of organic
residues on surfaces which can be identified by their NEXAFS spectra.
Other exciting applications of micro-NEXAFS lie in the study of chemi-
sorbed molecules on surfaces. Information can be obtained regarding nucleation
phenomena and domain formation. With a lateral resolution close to 100 Aone
may image individual domains and obtain information on azimuthal molecular
orientations, i.e., the orientation relative to the substrate registry, even for
substrates with higher than twofold symmetry. This information is lost in
conventional NEXAFS because of averaging over domains, as discussed in
Sect. 9.4.

11.2 Liquid Surfaces

Other improvements and new opportunities are created by the possibility of
manipulating the polarization of synchrotron radiation through insertion de-
vices. For example, the use of undulator sources is advantageous for conven-
tional NEXAFS studies in that it produces almost perfectly linearly polarized
(P ~ 0.99) X-rays [11.10]. If the electron beam undulates in the horizontal plane
the emitted X-rays are linearly polarized in that plane. Thus unwanted effects
arising from the finite vertical E vector component, present in elliptic-
ally polarized radiation from bending magnets and wigglers (Chap. 9), are
eliminated.
While solid samples can be rotated in the X-ray beam this is, in general, not
possible for liquids. For NEXAFS studies ofliquids and liquid surfaces it would
be highly desirable to develop insertion devices that allow the rotation of the E
vector from horizontal to vertical, such that the orientation of molecules can be
determined. Such devices have indeed been suggested! [11.11,12] and can be
expected to be available in the future.

1 A helical undulator which produces circularly polarized X-rays has been described by Elleaume
[11.13]. Two such devices producing right and left handed circularly polarized radiation, respect-
ively, may be arranged in series to produce linear polarization with variable E vector direction.
344 11. A Look into the Future

Polarization-dependent NEXAFS spectra ofliquid samples and surfaces can

be recorded using a similar arrangement as previously used for in situ catalytic
studies (Fig. 5.18). The sample is kept in a small chamber that is filled with a gas
(e.g., helium) and is separated by a window from the ultrahigh vacuum environ-
ment of the beam line. The beam is reflected down onto the surface and the
fluorescence yield of the sample serves as the NEXAFS signal. Problems of
interest range from the orientation of molecules at liquid surfaces, in general,
and systems like liquid crystals or membranes, in particular. For example, it
would be of interest to determine the orientation of fatty acids at liquid surfaces
[11.14] in analogy to the study of Langmuir-Blodgett films discussed in
Sect. 10.7.

11.3 Time-Resolved Studies

In Sect. 10.5.4 we discussed first results of time-dependent NEXAFS measure-

ments. NEXAFS spectra of pyridine on Ag(l11) [11.15] were continuously
recorded while the coverage on the surface was changed. It is clear from these
studies that time-dependent measurements are another interesting application
ofNEXAFS spectroscopy. An even more exciting possibility was revealed by the
work by Zaera et al. [11.16]. These authors showed that important kinetic
information can be derived by continuously monitoring resonance intensities as
a function of coverage and/or temperature. This was demonstrated by studying
the formation of ethylidyne from ethylene on Pt(111) as a function of temper-
ature. In this case the monochromator was set at a fixed photon energy
(285.8 eV) and the appearance of a resonance intensity that is absent for ethylene
but present for ethylidyne was monitored as a function of time at different
annealing temperatures.
In order to avoid possible problems associated with a change in background
intensity or intensity changes in the spectrum not related to reaction kinetics, it
is desirable to record complete NEXAFS spectra as a function of time, rather
than monitoring the intensity at one photon energy. The technique of choice
would consist of recording a complete NEXAFS spectrum in a single "snap-
shot" and studying the evolution in time in a movie-like fashion by continuous
snapshots. The question is how this can be done and in what time intervals.
The basic idea for accomplishing this is simple and has been used for decades
in optical spectrographs and more recently by Gerritsen et al. [11.17] in
conjunction with a laser plasma source to record entire EXAFS spectra in the
soft X-ray region in a single shot. One uses the continuous dispersion properties
of gratings and suitable X-ray optics to form a focused yet energy-dispersed
image of the X-ray source (or an entrance slit) on the sample. Thus different
spots (lines, in practice) on the sample correspond to different photon energies. If
the electron or photon yield generated in these different spots is imaged with
magnification onto a video screen the intensity pattern across the screen will
then reflect the NEXAFS spectrum of the sample. Thus the whole NEXAFS
 11.4 Monosized Cluster Ions 345

spectrum can be obtained in a single shot and the accumulation time for a
spectrum is mostly determined by the incident photon flux. This scheme, of
course, requires the sample to be homogeneous.
By use of a conventional undulator source the beam dimension on the
sample in the non-dispersive horizontal direction can be easily kept smaller than
1 mm. The beam is focused and dispersed in the vertical direction and the energy
dispersion across the sample depends on the line density of the grating. For
polarization-dependent NEXAFS experiments with the E vector in the horizon-
tal plane, the sample needs to be rotated about a vertical axis or the X-ray beam
direction. Rotation about the beam direction is more difficult and we shall not
consider it. For the conventional vertical rotation axis one needs an optical
design with a vertical focal plane, i.e., an erect field spectrograph. As discussed
by Hettrick [11.18] this may be achieved with a variable line density grating.
The final step is to image the signal from microscopic regions on the sample
onto a video screen. For electron detection, magnetic or electrostatic electron
optics similar to that required for micro-NEXAFS can be used [11.8, 9]. X-ray
fluorescence detection is more difficult. One could possibly use a microchannel
array with a large ratio of channel length (1 cm) to channel diameter (10 ~m) as
an X-ray guide to a position sensitive semiconductor diode detector (compare
Sect. 5.3.5). The field of view for each microchannel in such a device is very
limited and if the device is placed close to the sample one may achieve a
reasonable lateral resolution (~30 ~m). The microchannel array alone [11.19]
or in combination with a thin film filter may also be used to decouple the
vacuum environment of the diode from the sample cell which may be filled with
a gas.
How fast can we hope to record an entire NEXAFS spectrum for a
monolayer of carbon on a surface? With the above polychromator scheme the
photon flux on the sample per energy interval will be comparable to what one
can obtain with a conventional monochromator equipped with an exit slit. Thus
the counting time per point will also be the same, assuming that the electron
optical system does not cause significant loss. Most NEXAFS spectra at the C
K-edge in this book were recorded with a flux of about 3 x 109 photons/s, a
spectral resolution of about 1 eV and a total accumulation time per point of
about lOs. At the same spectral resolution one can expect about 10 14 photons/s
with an undulator source and a spherical grating monochromator at the
Advanced Light Source in Berkeley [11.20]. Since the accumulation time per
point scales inversely with flux, in the future one should be able to record an
entire NEXAFS spectrum of a chemisorbed monolayer in a millisecond. For
bulk samples or thin films accumulation times of about 10 ~s appear feasible.

11.4 Monosized Cluster Ions

One of the most exciting new applications of NEXAFS spectroscopy in chemis-

try and physics involves studies of monosized cluster ions, which range in size
346 11. A Look into the Future

from one to a few hundred atoms. Measurements of the electronic and crystallo-
graphic structure of cluster ions as a function of cluster size would provide a
wealth of information regarding the elemental bonding-structure relationship of
matter [11.21]. In order to avoid artifacts, such studies are best done on free
clusters. Because of the difficulty of producing a large density of selected
monosized clusters such experiments are severely demanding in terms of photon
flux and require the most advanced X-ray sources.
It has been proposed by Yarmoff [11.22J that K-shell excitation spectra of
gas phase cluster ions may be obtained by use of ion cyclotron resonance (ICR)
spectroscopy, also known as Fourier transform mass spectrometry [11.23]. The
idea is to record the total ion yield, consisting of all ions that differ in mass or
charge from the original cluster ions. Although the total ion yield will typically
not follow the X-ray absorption coefficient quantitatively, especially in the
bound state region, it can still be used for structural identification. The reason is
that it still exhibits all resonances present in the X-ray absorption coefficient
[11.24-26J, and the differences in intensities are of secondary importance. In
addition, the ICR technique allows one to simultaneously record the intensities
of all individual ions generated through X-ray absorption, and therefore gives
information on the deexcitation and fragmentation process.
The experimental arrangement would consist of placing the trapped ion cell
of an ICR apparatus at the focus of the monochromatic X-ray beam. Choosing
the X-ray propagation direction along the magnetic field optimizes the inter-
action volume. Calculations of the expected signal level for the cluster experi-
ments are quite favorable if we use the monochromatic photon flux calculated
for an undulator on a third generation ring. For example, the Advanced Light
Source in Berkeley equipped with a U5 undulator and a spherical grating
monochromator is expected to deliver 5 x 10 13 photons/s with an instrumental
energy resolution of 25 meV at a photon energy of 295 eV [11.20J.
Let us calculate the expected signal for carbon clusters. The cross section
per atom for absorption above the C K-edge (Fig. 5.11) is about 1 Mb or
1O- 16 mm 2 • The ICR apparatus can trap between 104 to 106 ions in a volume of
about 1 mm 3 and the detection sensitivity is better than 0.1 %. In order to
minimize multiple excitations of the same cluster, only about 1% of the trapped
clusters can be excited before the trap is cleared and the ion products analyzed.
For 105 trapped 10-C-atom cluster ions one would therefore be limited to 103
absorption events. Using a flux of 10 13 photons/(smm 2 ) this is accomplished in
1 s. Each cluster ion that absorbs a photon with energy in excess of the I sIP will
lose at least one electron. It will become multiply charged or dissociate by
Coulomb explosion [11.24, 27]. We can therefore in Is generate 10 3 modified
cluster ions, consisting of all species that are different in mass or charge from the
originally trapped 10-C-atom cluster ions. In order to obtain a signal-to-noise
ratio of 100 we would have to repeat the process consisting of filling the trap,
exposure to the beam for 1 s, and clearing/reading the products, 10 times. A
complete absorption spectrum, consisting of 200 photon energy points could
therefore be recorded in one hour.
 11.5 Molecular Subgroups in Complex Environments 347

It is clear that we have only described the simplest possible experiment.

Many variants are possible, such as recording the ion yield spectra ofthe various
fragments created. More generally, one may choose various cluster ion systems,
e.g., molecular adsorbates attached to metal cluster ions. A big advantage of the
ICR is the ability to measure negative ions as easily as positive ions. This will
enable the elucidation of mechanisms which result in the formation of negative
ions in the gas phase.
An early example of what spectra of complex carbon clusters may look like is
shown in Fig. 11.1, where the spectrum of benzene is compared to that of
Buckminsterfullerence, C 60 [11.28], the structure of which is shown in the inset
[11.29]. The sample used for this study consisted of a thin film of C 60 deposited
on a Si wafer as described by Bethune et al. [11.30].

Fig. 11.1. ISEELS spectrum of benzene gas [11.31]

and NEXAFS spectrum of solid C60 [11.28]. The struc-
ture of C60 is shown in the inset. Note the detailed fine
280 290 300 310 320 structure for C60 which typically is only found for free
Excitation Energy (eV) molecules and not for solids

11.5 Molecular Subgroups in Complex Environments

NEXAFS by means of fluorescence detection requires a factor of 1000 more flux

than by electron yield detection, as discussed in Sect. 5.4. One may even go a step
further and not integrate over the total K-shell fluorescence signal but resolve
the various fluorescence lines with a suitable second monochromator [11.32,
33]. Similar to Auger spectra high resolution fluorescence spectra of molecules
are rich in structure and the various lines correspond to transitions between
occupied molecular orbitals and the K-shell. In contrast to the Auger spectra,
however, fluorescence spectra are simpler in that they are dictated by dipole
selection rules. Thus relatively sharp lines can be identified which correspond to
348 11. A Look into the Future

transition from well-defined MOs to the K-shell [11.34]. Also, for oriented
molecules the transition intensities exhibit a pronounced polarization depend-
ence [11.35]. For complex macromolecules transitions corresponding to specific
functional subgroups, e.g., a C=O triple bond, may be distinguished from those
corresponding to other subgroups. This offers the opportunity of recording
NEXAFS spectra of specific functional subgroups by monitoring the intensity of
the fluorescence line(s) associated with the subgroup as a function of excitation
energy.
As an example consider an investigation of the bonding of O 2 in myoglobin
(Fig. 1.1). A conventional NEXAFS spectrum at the 0 K-edge would average
over the various 0 atoms in the macromolecule contained in C-O bonds, and
the signature of the O 2 molecule would be buried. With fluorescence detection
the molecule can be studied in its natural state (no vacuum required), and by
monitoring the intensity of a fluorescence line characteristic of the O 2 group its
NEXAFS spectrum can be recorded.
Nordgren et al. [11.34] have shown the feasibility of such experiments by
using a spherical grating monochromator to analyze the fluorescent radiation
from gas and solid samples. Their experiments were conducted using a high flux
plane grating monochromator beam line on a wiggler source at HASYLAB. It
appears that experiments on bulk samples and thin films, e.g., polymer films on
surfaces, should be straightforward, but that, even with the most advanced
sources, studies of organic monolayers on surfaces may still be marginal.
Appendices

A. Derivation of the EXAFS Equation

In calculating the EXAFS signal we start from the definition of the X-ray
absorption cross section given by (2.8), which in the "length" form, see (2.11), can
be written as

(A.1)

where C is a constant, and we have assumed that the density of states factor in
(2.8) has been incorporated into the wavefunction normalization. For an iso-
lated atom this cross section, above the absorption edge, will exhibit a smooth
energy dependence because the final state wavefunction If) is well behaved and
its overlap with the initial state changes smoothly. For a molecule or a solid, the
final state wavefunction is of more complicated nature because it contains terms
which arise from the back scattering of the photoelectron wave by the neighbor
atoms.
As the kinetic energy of the excited photoelectron becomes large relative to
its interaction energy with the valence electrons of the surrounding atoms (a few
eV) the scattering by the neighbor atoms is largely determined by their atomic-
like core potentials. We can then use the approximation that the scattering off
the neighbors is a simple sum of their isolated contributions. In this single
scattering picture multiple scattering between several centers is ignored, and all
the physics is contained in the proper description of the final state wavefunction
If) for a diatomic. Larger systems can be treated by a building block principle.
In a simple but correct picture the final state wavefunction contains two parts,
an atomic-like component 'I'at(r), which is the original outgoing photoelectron
wave, and a scattered component 'I'sc(r), which is thrown back at the central
atom by the neighbor atom, according to

(A.2)

where the coordinate r refers to the central atom. Since the dipole matrix
element is evaluated on the central atom, and its dominant contribution arises
from the volume occupied by the Is core, one can think of EXAFS as a
scattering experiment where the central atom acts as the "source" as well as the
"detector" for the photoelectron.
350 Appendices

The scattering problem at hand is illustrated and defined in Fig. A.1. In

order to be able to use partial wave scattering theory with appropriate bound-
ary conditions we set up the potential in a muffin-tin form (Sect. 2.7.3) by
surrounding the central atom A and the neighbor atom B by spheres I and III of
radius a and b, respectively, and denote the internuclear distance by Ro, as

(a)

(d) EXAFS Photoelectron Diffraction

2
• 13r",' •
A B

/ .n
•A I
_/3
B

Fig. A.1. (a) Partition of space for a diatomic molecule consisting of atoms A and B separated by an
internuclear distance Ro. The atoms are surrounded by spheres with radii a and b, respectively,
resulting in regions I, II and III. (b) The molecular potential for the spatial division shown in (a) is of
the muffin-tin form and is spherically symmetric in regions I and III, and constant (the inner
potential Vo < 0) in region II. (e) Coordinate systems for describing the EXAFS scattering process.
The coordinate systems (x, y, z) on the central excited atom A and (x', y', z') on the scattering atom
B are oriented with oppositely oriented z- and z'-axes, parallel to the internuclear vector Ro. The x-
and x' -axes are rotated such that the position vectors r about atom A and r' about atom B have the
same azimuthal spherical angles 4> = 4>'. The electric field vector E of the X-rays lies in the (x, z)-
plane, at an angle (Jo from the z-axis. (d) Schematic of the scattering processes for EXAFS and
photoelectron diffraction. The dashed arrow signifies the original atomic-like wave, the solid arrows
indicate the path of the scattered wave. The EXAFS process is equivalent to the sum of the two
photoelectron diffraction processes shown, when they are integrated over the emission angle Q
 A. Derivation of the EXAFS Equation 351

illustrated in Fig. [Link]. This leads to a potential (2.58) which is schematically

shown in Fig. [Link]. The potential is spherically symmetric inside the muffin-tin
spheres I and III and constant (the inner potential Vol in region II. We now
define coordinate systems (x, y, z) on atom A and (x', y', z') on atom B. In the
two coordinate systems we use spherical coordinates (r, 4J, 0) and (r', 4J', 0'),
respectively. Furthermore, we choose the coordinate axes such that, at a general
point P, we have

4J = 4J' , (A.3)

rsinO = r'sinO' , (AA)

rcosO + r'cosO' = R o , (A.5)

and

(A.6)

We further assume linearly polarized X-rays. Because the molecule has cylindri-
cal symmetry about the z-axis there cannot be an azimuthal polarization
dependence, and without loss of generality we choose E = Ee in the (x, z )-plane,
where 00 is the polar angle between E and the internuclear z-axis. The dipole
operator in (A.I) can then be written as

e'r = r(sinOosinOcos4J + cos 00 cos 0) . (A.7)

If we introduce orthonormal spherical harmonics Yj( 0, 4J) [A.1],

o
Y1 = -Jf3
41t cos 0 , (A.8)

yl = _ (3 sin OeitJ>
1 -J8ii ' (A.9)

and

y-l =
1
f3 sinOe-itJ> '
-J8ii (A. 10)

(A.7) can be rewritten as

(A. 11)

Because of the dipole selection rule this choice also defines the form of
the angular dependence f( 0, 4J) of the photoelectron wave created on atom
A. For K-shell excitation the initial state is spherically symmetric
352 Appendices

Ii) = ygR ls = JI/(4n)R ls , and the general angular dependence for the 1=1
final state is given by
+1
J«(),¢)= L
m=-l
amy~, (A.12)

where the coefficients may be complex. By considering the matrix element in

(A.1), and by normalizing the angular wavefunctionJ«(), ¢) to unity, we obtain

(A. 13)

Since Yl 1 - y~ oc sin () cos ¢, and y~ oc cos (), the photoelectron distribution

has a maximum in the (x,z)-plane (¢ = 0°), and a node along the y-axis
«() = ¢ = 90°).
The radial part of the atomic-like component lJ'at is, in principle, obtained by
solving the Schrodinger equation in region I. Fortunately, it is not necessary to
do so in deriving the EXAFS equation. We just assume that a solution exists and
call it u(r, E), where E is the kinetic energy of the photoelectron, measured from
the vacuum level. We then simply assume that the function

lJ'at(r) = lJ'!t(r) = u(r, E)J«(), ¢) (A.14)

is of good quality such that it accurately describes the atomic X-ray absorption
cross section according to
(A.15)

In order to describe IJ'se we need to know the form of the I = 1 radial part
R 1 (r) of IJ'at in region II. Since in this region the potential is a constant, with a
value of Vo < 0 relative to the vacuum level, the most general radial solution to
the Schrodinger equation which is real can be expressed as a linear combination
of spherical Bessel functions Mkr) and spherical Neumann functions n,(kr)
[A.2], and the I = 1 component is given by [A.3]

(A.16)

Here B is a constant, and the photoelectron wavevector k is given by

(A.17)

where 2m/h 2 = 0.2625 A-2 eV- 1 , and the "zero" of the photoelectron kinetic
energy is at E = Vo below the vacuum level. The central atom phase shift
h1 = h1(k) is derived by matching the wavefunctions u(r, E) and R1(kr) and
their derivatives across the muffin-tin sphere between regions I and II [A.3].
Clearly the determination of h 1 (k) requires knowledge of u( r, E), and it is
 A. Derivation of the EXAFS Equation 353

derived in practice by a self-consistent calculation [A.4]. The beauty of partial

wave scattering theory is that the phase shifts completely determine the
scattering processes. We will demonstrate this below.
We can rewrite (A.16), which has the real form of a standing wave, as a sum
of complex "incoming" and "outgoing" waves. This is conveniently done by use
of spherical Hankel functions. We follow Schiff [A.2] and define

h,(kr) = hj1>(kr) =j,(kr) + in,(kr) , (A.18)

where hj1>(kr) is a spherical Hankel function of the first kind. The 1= 1

component of the "outgoing" wave is then given by

(A.19)

and the "incoming" wave is described by its complex conjugate

(A. 20)

such that

(A.21)

From (A.21) we can deduce ourfirst theorem of partial wave scattering theory:
When a partial wave solution of the Schrodinger equation outside the potential
of a reference atom characterized by phase shifts (j, is written in terms of an
"incoming" and an "outgoing" wave then the "incoming" and "outgoing" waves
have the same magnitude and symmetry, but differ by a phase shift ei2b ,.
Since hi (kr) has the form of an outgoing wave relative to the central atom we
shall write our general atomic-like component Pat(r) in region II as

(A.22)

where, for convenience, we have defined A = B/2.

We now consider the scattered wavefunction p. c • Since the scattering by
atom B will be strongest near its core where the electron density is largest we
make the approximation that the scattering by atom B can be accounted for by
considering a spherical scattering center which is small compared to the
interatomic distance Ro, the so-called small atom approximation. In general, one
can approximate the scattering by a small center in various ways [A.5-7], and
we shall make the particular approximation of an infinitely small scattering
center. Then the curvature of the wavefront, and the change in amplitude and
phase of the wave across the region of the potential, can be neglected. In other
words, for a realistic spherical potential of finite range, in this approximation,
the incident wave will have the exact value only at the center of the potential,
354 Appendices

point B in Fig. A.I. This value is given by the amplitude ofthe atomic-like wave
(A.22) at r = R o, i.e., J3/81t Ahl (kR o)ei6, • Because the curvature of the wave-
front can be neglected across the point potential we can simply write for the
wave incident onto the scattering potential

1[111
at
(r') -- vs;;,
(3 Ah (kR )e
1 0
i61 e ik · r '
, (A.23)

which is a plane wave with the proper amplitude and phase of the original
spherical wave. Here the wave propagation direction k is in the direction of R o.
We can now follow the partial wave scattering treatment found in standard
quantum mechanics texts, e.g., [A.8], and expand the plane wave as a partial
wave sum according to

I
00
e ik · r ' = eikr'cosa = (21 + IWil(kr')PI(cosa) , (A.24)
1=0

where a = 1t - f)', and PI(cosa) are Legendre polynomials. We next need to

describe the scattering of the wave given by (A.23) by the potential of atom B.
Again, the scattering is completely determined by the phase shifts 81 associated
with that potential. The phase shifts are derived in the same way as discussed
earlier for the phase shifts hi of the central atom by assuming a muffin-tin-like
potential and matching the wavefunctions across the sphere boundary. With
knowledge ofthe 8 1'S we can account for the scattering of the partial wavesil(kr')
in (A.24). According to (A.18), we can write

il(kr') = Hhl(kr') + ht(kr')] , (A.25)

and this form underscores thatil(kr') is indeed unscattered by the potential of

atom B since the "ingoing" and "outgoing" parts have no phase shift difference.
On scattering by the potential of atom B, this changes and according to the first
partial wave theorem, stated earlier, the "ingoing" and "outgoing" waves relative
to atom B need to differ by a phase shifts ei2 .,. From the first theorem we know
that a solution to the SchrOdinger equation in region II must then have the form

0l(kr') = ![h l (kr')e i2 .. + hr(kr')] , (A.26)

such that the effect of the potential of atom B is properly included through the
phase shift term. We can view 0l(kr') as a sum of an unscattered component
il(kr'} and a scattered component SI(kr'), and by use of (A.25) and (A.26)
determine

SI(kr') = 0l(kr') - il(kr') = !hl(kr') [e i2e , - 1] . (A.27)

This result for the scattered wave expresses our second theorem of partial
wave scattering theory:
 A. Derivation of the EXAFS Equation 355

The scattering of partial wavesj,(kr') by a potential characterized by phase

shifts 8, is expressed by the transformation

(A.28)

Note that there is a phase as well as an amplitude change upon scattering.

Making the substitution given by (A.28) in (A.24) yields the following expression
for the scattered wave emanating from atom B:

(A.29)

All information on the scattering process is contained in the term

(A.30)

By setting IX = n, i.e., considering only backscattering, and by assuming that the

spherical wave i' h,( kr') can be approximated by its asymptotic limit eikr ' j(ikr'),
we obtain
ikr'
t(k, IX, r') = : . , t(k, n) , (A.31)
r
where
1 '",ax
t(k, n) = - .
21k '=0
L (21 + 1)(ei2 £. - 1)( -1)' (A.32)

is the familiar plane wave backscattering factor of atomic physics [A.8, 9]. In
(A.32) we have omitted terms with I> Imax since in reality all partial wave
amplitudes may be neglected if I > Imax ~ kb [A.3], where b is the range of the
scattering potential, or about the radius of the muffin-tin sphere around atom B.
In the EXAFS literature it is common to write the complex scattering amplitude
in terms ofa real amplitude F(k) and a real phase shift P = P(k) characteristic of
the scattering atom B, i.e., t( k, n) = F( k )e ifJ , yielding

(A.33)

The scattered wave given by (A.33) refers to the coordinate system (x', y', Zl)
centered at atom B. As is evident from (A.32) it contains all partial wave
components. In order to consider its interference with the atomic-like wave
'l'at(r) according to (A.2) we need to express it in the coordinate system (x, y, z).
This is done by use of the "L6wdin IX-expansion" [A.10]. Only the 1 = 1 term
needs to be considered in the expansion of the scattered wave at atom A because
only this partial wave will interfere with the atomic-like wave which has 1 = 1.
356 Appendices

For the expansion we make the ansatz

+1
'I'!~(r') = 'I'!~(r) = L IXm Y'f( 0, <fJ) .
m=-l
(A.34)

The r- and k-dependent coefficients ~ are determined by multiplying both sides

of (A.34) by the sum of the complex conjugate spherical harmonics and by using
their orthonormality. We obtain, IX-I = IXl = 0 because the <fJ-integration
vanishes, and

2""
IXo = ~
-4 J J'I'!~(r')cosOsinOdOd<fJ.
1t 0 0
(A.35)

By using (A.6) we find sin 0 dO = r' dr' /( r Ro) and, replacing the integration over
oby an integration over r', we obtain
I31t Ro+r
IXo = V J/t 2 J 'I'!~(r') [r2 + R~ - (r')2] r' dr' . (A.36)
2( rR o) Ro-r

Substituting (A.33) into (A.36) allows the integral to be evaluated as

IXo = ~ikA[hl(kRo)FF(k)[Link](kr). (A. 37)

The radial dependence of the resulting scattered wave 'I'!~(r) = IXo Y~ about the
central atom is therefore given by a spherical Bessel function jl(kr). We can
account for the modification of this function by the central atom potential by
use of the first theorem, and in analogy to (A.26) we know that the function

(A.38)

is a solution to the Schrodinger equation which incorporates the effect of the

central potential. In calculating the interference with the atomic-like component
which is expressed as an "outgoing" wave relative to atom A, (A.22), we need to
take the "outgoing" component of (A.38). Thus we can simply make the
replacement

jl (kr) -+ thl (kr)e i2 .J , (A.39)

in (A.37). This yields the following final result for the scattered wave:

(A.40)

The complete final state wavefunction in region II, according to (A.2), is

therefore given by combining (A.22) and (A.40), i.e.,

(A.41)
 A. Derivation of the EXAFS Equation 357

where

(A.42)

In order to calculate the cross section according to (A.1) we need to know

If) in region I, where its overlap with the 1s core function is largest. We have
already considered earlier how to match across the muffin-tin sphere between
regions I and II for the atomic-like component, and the results in the two regions
are given by (A.14) and (A.22), respectively. Because the composite wave given
by (A.41) has the same analytical form in region II as the atomic-like component,
it will possess the same form also in region I, i.e.,

If) = u(r, E)[f(O, l/J) + XY?J , (A.43)

and by use of(A.1S) we can now evaluate the matrix element and obtain for the
cross section

(A.44)

Since the term X is the perturbation to the total cross section induced by the
backscattering process from atom B, we have IXI ~ 1 and the EXAFS signal, to
first order in the scattering, is given by

(1 -(1 M
X(k)= x 0=2y2cos 2 0oReX. (A.4S)
(10

At large photoelectron wavevector we have kRo ~ 1 and with h1 (kRo)-+

-eikRo/(kRo) we obtain the polarization-dependent EXAFS formula,

3 cos 2 0 .
X(k) =- kR~ 0 F(k)sm( 2kRo + 2«5 1 + {3). (A.46)

Here we have not yet accounted for thermal vibrations and inelastic scattering
effects. Using a Gaussian thermal disorder with a mean-square relative displace-
ment (12 and an electron mean free path A( k) we obtain the EXAFS of an
assembly of atoms by summing contributions from all atoms j in shells i of equal
distance R i ,

Finally, a few comments are in order regarding the relationship between

EXAFS and the extended fine structure observed in angle-resolved [[Link]] and
angle-integrated [A.12] photoelectron diffraction (PhD). This topic has been
considered theoretically by Lee [A.13] and Barton and Shirley [A.6, 14]. The
physical processes underlying the two techniques are illustrated in Fig. A.1d.
358 Appendices

Here we show as dashed arrows the atomic-like outgoing wave of the photo-
electron whose interference with the scattered wave, shown as solid arrows, is to
be considered. Using the example of a diatomic, it is straightforward to represent
the different scattered waves. In EXAFS the "detector" is at the central atom
position and the scattered wave is simply that backscattered from atom B. In
PhD the detector is located at a solid angle Q with respect to the internuclear
axis and the interference of the atomic-like wave and the scattered waves need to
be considered at the detector position. For a diatomic, there are two scattering
processes that dominate. The first, shown as an arrow with the label "2" in
Fig. [Link], involves back scattering from atom B, followed by scattering at the
central atom into the detector direction. The second process, represented by an
arrow marked "3", involves scattering by atom B into the direction of the
detector. As shown by Lee [A.15], consideration of the two scattering processes
"2" and "3", and integration over the whole solid angle, leads to the EXAFS
equation. Thus in the limit of integrating over 4n, photoelectron diffraction and
EXAFS are identical. The other interesting point revealed by the above com-
parison is that EXAFS, when discussed in terms of PhD processes, actually
includes multiple scattering, namely process "2".
 B. Chemisorbed Molecules Studied by NEXAFS 359

B. Chemisorbed Molecules Studied by NEXAFS

Molecule Name Substrate Reference

Chemical
formula

C-H bonds
CH 30H Methanol Mo(llO) B.l

N-H bonds
NH3 Ammonia Ni(llO) B.2
Fe B.3
KjFe B.3

O-H bonds
H 2O Water Ru(OOI) B.4

S-H bonds
H 2S Hydrogen sulfide Ni(I00) B.5
Cu(I00) B.6

C-C bonds
C2 Dicarbon Ag(110) B.7,8
C 2H 2 Acetylene Pt(lll) B.9,10
Ni(lll) [Link]
Cu(I00) B.12, 13
Ag(I00) B.13,14
Ag(llO) B.7
C 2H 4 Ethylene Pt(lll) B.9, 15-18
Ni(1ll) [Link]
Cu(I00) B.l2-14, 19,20
Ag(I00) B.13, 14, 19
Ni(I00) B.21
Ag(llO) B.22
Pd(lll) B.23
C 2H 6 Ethane Cu(I00) B.12-14
Ag(I00) B'13
C 3H4 Allene Ag(110) B.24
C 3H4 Methylacetylene Ag(110) B.24
C3H 6 Propylene Ag(llO) B.22
C 4H 6 Butadiene Ag(llO) B.25
Mo(I00) B.26
Mo(llO) B.27
C4H 6 Cyc10butene Pt(lll) B.1O
C4 H S Cyc10butane Pt(lll) B.28
CsHs Cyc10pentene Pt(lll) B.1O,28
C6 H 6 Hexatriyne Ag(llO) B.24
C6 H 6 Benzene Pt(lll) B.29,30
Cu(llO) B.31
Cu(lll) B.31
Ag(lll) B.32
Mo(110) B.33,34
Ag(llO) B.34,35
360 Appendices

Molecule Name Substrate Reference

Chemical
formula

Pd(ll1) B.36
Ni(lll) B.37
Ni(llO) B.38,39
C 6 H12 Cyc10hexane Pt(lll) B.9,28
C 7H S Toluene Pt(lll) B.29
C 7H S Cyc10heptatriene Pt(lll) B.9,lO
CsHs Cyc100ctatetraene Pt(lll) [Link], 28
CIOHs Naphthalene Ag(111) B.32
C 14H IO Anthracene Ag(lll) B.32,4O
C 1s H 12 Tetracene Ag(lll) B.32
Cu(lOO) B.32
C 12 H 12 Perylene Ag(lll) B.32
Cu(lOO) B.32
C 24 H 12 Coronene Ag(111) B.32

C-N bonds
CN Cyanide Pd(l1 1) B.4l,42
HCN Hydrogen cyanide Pt(lll) [Link]
Pd(lll) B.42
(5 x 1) CjW(lOO) B.43
C 2N 2 Cyanogen Pd(lll) B.42
Ag(llO) B.24
CH 3CN Acetonitrile Pt(lll) [Link]
Ag(llO) B.44
Au(lOO) B.45·
CH 3 NC Methyl isocyanide Pt(lll) [Link]
C 3 H 3N 3 s-Triazine Cu(lll) B.3l
Cu(llO) B.46
C 4H 4N 2 Pyrazine Cu(llO) B.3l,46
CU(lll) B.3l
Ni(lll) B.37
CsHsN Pyridine Pt(lll) B.29, 30,47
Cu(110) B.3l,46
Cu(lll) B.3l
Ag(l1l) B.48
Mo(llO) B.27
Ag(llO) B.24
Ni(lll) B.37
C 4H 4NH Pyrrole Pt(ll1) B.49
Mo(llO) B.27
C SH 6 NH N-Methylpyrrole Pt(l1l) B.49
C 6 H SNH2 Aniline Ag(110) B.35
C 6 H sCN Benzonitrile Pt(ll1) B.29

N-N bonds
N2 Nitrogen Ni(lOO) B.50
Ni(110) [Link]
Fe(l1 1) B.S2,53
Pt(ll1) B.S4
Graphite B.S5
 B. Chemisorbed Molecules Studied by NEXAFS 361

Molecule Name Substrate Reference

Chemical
formula

C-O bonds
CO Carbon monoxide Ni(lOO) B.50, 56--58
Cu(lOO) B.59-62
Ni(lll) B.63,64
Pt(lll) B.65
Fe(lOO) B.66,67
Pd(lll) B.41
Mo(lOO) B.68
Mo(llO) B.69
Pt(533) B.70
NajPt(lll) B.65
KjCu(IOO) B.61
KJNi(111) B.64
(5 x 1) CjW(lOO) B.43,71
H 2 jPt(1l1) B.72
Al(lll) B.73
CO 2 Carbondioxide Ni(llO) B.74
C0 3 Carbonate Ag(llO) B.75,76
CH 3 0H Methanol Cu(l00) B.59, 77, 78
Cu(llO) B.79
Si(lll) B.80
Mo(IlO) B.1
C 2 H sOH Ethanol Cu(llO) B.81
C 3 H 7 OH Propanol Si(Il1) B.80
C 3 H sOH Allyl alcohol Si(Il1) B.80
Ag(llO) B.82
C 3 H 3 OH Propargyl alcohol Si(ll1) B.80
Ag(llO) B.82
HCOOH Formic acid Cu(lOO) B.59, 77, 83
Cu(110) 8.60,84,85
Si(111) B.80
Ag(llO) B.86
C 2 H sCOOH Propanoic acid Si(111) B.80
C 2 H 3 COOH Acrylic acid Si(lll) B.80
C 2 HCOOH Propiolic acid Si(111) 8.80
C4 H 4 O Furan Mo(llO) B.27
Ag(110) B.87
C4 H 6 O 2,5-Dihydrofuran Ag(110) B.87
C4 H 2 0 3 Maleic anhydride Ag(llO) 8.88
C6 H sOH Phenol Mo(llO) B.89
Ag(llO) B.35

N-O bonds
NO Nitrogen monoxide Ni(l00) B.50, 56, 90
Pd(lll) B.41
OjNi(l00) B.9O
Pd(110) B.91
N0 2 Nitrogen dioxide Ni(lOO) 8.92
362 Appendices

Molecule Name Substrate Reference

Chemical
formula

C-F bonds
CF 3 CN Trifluoroacetonitrile Pt(lll) [Link]
C6 F 6 Hexafluorobenzene Pt(lll) B.29

0-0 bonds
O2 Oxygen Pt(lll) B.59, 93, 94
Ag(llO) B.62,93
Si(lll) B.95
KjRu(ool) B.96
Graphite B.97

C-S bonds
CH 3 SH Methanethiol Pt(lll) B.98
C4 H 4 S Thiophene Pt(lll) B.99,100
Ni(loo) B.101
Cu(lll) B.102
Mo(llO) B.27
C 6 H sSH Benzenethiol Mo(llO) B.103,104

o-s bonds
S02 Sulfur dioxide Ag(llO) B.105
References

Chapter 1
1.1 L. Stryer: Biochemistry (Freeman, New York 1988)
1.2 M. Van Hove, W. Weinberg, C.-M. Chan: Low-Energy Electron Diffraction, Springer Ser. Surf.
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1.5 G. Ertl: J. Vac. Sci. Technol. 1, 1247 (1984)
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1.7 P.H. Citrin: J. de Phys., Colloq. C8, 437 (1986)
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1.22 G. Comelli, J. Stohr: Surf. Sci. 200, 35 (1988)
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1.35 A.L. Johnson, E.L. Muetterties, J. Stohr: J. Am. Chern. Soc. lOS, 7183 (1983)
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1.43 RJ. Koestner, J. Stohr, J. L. Gland, E.B. Kollin, F. Sette: Chern. Phys. Lett. 120, 285 (1985)
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1.50 A.P. Hitchcock: J. de Phys., Colloq. C8, 575 (1986)
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1.52 A.P. Hitchcock, J.A. Horsley, J. Stohr: J. Chern. Phys. 85, 4835 (1986)
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1.62 G. Tourillon, A. Fontaine, Y. Jugnet, Tran Minh Duc, W. Braun, J. Feldhaus, E. Holub-
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1.63 G. Tourillon, A. Fontaine, R. Garrett, M. Sagurton, P. Xu, G.P. Williams: Phys. Rev. B 35,
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Chapter 3
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Chapter 4
4.1 For a review ofiSEELS see:
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4.73 M.B. Robin, I. Ishii, R. McLaren, A.P. Hitchcock: J. Electron Spectrosc. 47, 53 (1988)
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J.L. Dehmer: J. Chern. Phys. 56, 4496 (1972)
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violet, ed. by S.P. McGlynn, G. Findley, R. Huebner (Reidel, Dordrecht 1985)
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4.117 E.A. Stern: Phys. Rev. Lett. 49,1353 (1982)
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4.138 E. Ruhl, A.P. Hitchcock: Chern. Phys. 154, 323 (1991)
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4.140 A.P. Hitchcock, C.E. Brion: J. Phys. B 14, 4399 (1981)
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Special Pub!. Nos. 11 and 18 (The Chemical Society, London 1958, 1965)

Chapter 5
5.1 R.F. Egerton: Electron Energy-Loss Spectroscopy in the Electron Microscope (Plenum,
New York 1986)
5.2 B.K. Teo, D.e. Joy (eds.): EXAFS Spectroscopy, Techniques and Applications (Plenum,
New York 1981)
5.3 D. Sayre, J. Kirz, R. Feder, D.M. Kim, E. Spiller: Ultramicroscopy 2, 337 (1977)
5.4 For a review of ISEELS spectra of surfaces see: M. De Crescenzi: CRC Crit. Rev. Solid State
Mater. Sci. IS, 279 (1989)
5.5 Z.L. Wang, J.M. Cowley: Surf. Sci. 193, 501 (1988)
5.6 T. Tyliszczak, F. Esposto, A.P. Hitchcock: Phys. Rev. Lett. 62, 2551 (1989)
5.7 T. Tyliszczak, A.P. Hitchcock: J. Vac. Sci. Technol. A 8, 2552 (1990)
5.8 R.L. Johnson: In Handbook on Synchrotron Radiation, Vol. la, ed. by E.E. Koch (North-
Holland, Amsterdam 1983) p. 173
5.9 M.R. Howells: Nucl. Instrum. Methods 172, 123 (1980)
5.10 J.B. West, HA Padmore: In Handbook on Synchrotron Radiation, Vol. 2, ed. by G.V. Marr
(North-Holland, Amsterdam 1987) p. 21
5.11 F. Sette, e.T. Chen: Rev. Sci. Instrum. 60, 1616 (1989);
C.T. Chen, F. Sette: Phys. Scr. T31, 119 (1990)
 References 375

5.12 M.O. Krause: J. Phys. Chern. Ref. Data 8, 307 (1979)

5.13 M.H. Chen, B. Crasemann, H. Mark: Phys. Rev. A 24, 177 (1981)
5.14 T.A. Carlson, RM. White: J. Chern. Phys. 44,4510 (1966)
5.15 M.L. Knotek, PJ. Feibelman: Phys. Rev. Lett. 40, 964 (1978);
PJ. Feibelman, M.L. Knotek: Phys. Rev. B 18, 6531 (1978)
5.16 R. Jaeger, J. Stohr, R. Treichler, K. Baberschke: Phys. Rev. Lett. 47, 1300 (1981);
R. Jaeger, R. Treichler, J. Stohr: Surf. Sci. 117, 533 (1982)
5.17 R. Treichler, W, Riedl, W. Wurth, P. Feulner, D. Menzel: Phys. Rev. Lett. 54, 462 (1985)
5.18 e.T. Chen, RA. DiDio, W.K. Ford, E.W. Plummer, W. Eberhardt: Phys. Rev. B 32, 8434
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5.19 W. Wurth, e. Schneider, R Treichler, E. Umbach, D. Menzel: Phys. Rev. B 35, 7741 (1987)
5.20 D. Menzel, P. Feulner, R. Treichler, E. Umbach, W. Wurth: Phys. Scr. T17, 166 (1987)
5.21 W. Eberhardt: Phys. Scr. T17, 28 (1987)
5.22 J. Stohr, R. Jaeger: Phys. Rev. B 26, 4111 (1982)
5.23 L.P. Wang, W.T. Tysoe, R.M. Ormerod, R.M. Lambert, H. Hoffmann, F. Zaera: J. Phys.
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5.24 R.Z. Bachrach, A. Bianconi: In Proceedings of the Fifth International Conference on Vacuum
Ultraviolet Radiation Physics, ed. by M.e. Castex, M. Pouey, N. Pouey, Montpellier, France,
1977, Vol. II, p. 213 (unpublished)
5.25 J. Stohr, e. Noguera, T. Kendelewicz: Phys. Rev. B 30, 5571 (1984)
5.26 I. Lindau, W.E. Spicer: J. Electron Spectrosc. 3, 409 (1974)
5.27 e.J. Powell: Surf. Sci. 44, 29 (1974)
5.28 WJ. Veigele: At. Data Tables 5, 51 (1973)
5.29 B.L. Henke, P. Lee, TJ. Tanaka, RL. Shimabukuro, B.K. Fujikawa: At. Data Nucl. Data
Tables 27, 1 (1982)
5.30 H. Tokutaka, K. Nishimori, H. Hayashi: Surf. Sci. 149, 349 (1985)
5.31 W. Gudat: Ph.D. Dissertation, Universitiit Hamburg (1974); DESY Report F41-74/10, DESY,
Hamburg, 1974 (unpublished)
5.32 R.G. Jones, D.P. Woodruff: Surf. Sci. 114,38 (1982)
5.33 M. Born, E. Wolf: Principles of Optics (Pergamon, London 1959)
5.34 Tables of optical constants in the VUV region:
H.-J. Hagemann, W. Gudat, e. Kunz: DESY Report SR-74/7, DESY, Hamburg, 1974
(unpublished);
R.-P. Haelbich, M. Iwan, E.E. Koch: In Physik Daten/Physics Data, ed. by H. Behrens, G. Ebel
(Zentralstelle fiir Atomkernenergie Dokumentation. Eggenstein-Leopoldhafen 1977);
J.H. Weaver, e. Krafka, D.W. Lynch, E.E. Koch: In Physik Daten/Physics Data, ed. by
H. Behrens, G. Ebel (Zentralstelle fiir Atomkernenergie Dokumentation, Eggenstein-
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5.35 B.L. Henke: Phys. Rev. A 6, 94 (1972)
5.36 O. Hachenberger, W. Bauer: In Advances in Electronics and Electron Physics, Vol. 11, ed. by
L. Marton (Academic, New York 1959) p. 413
5.37 R.H. Ritchie, F.W. Garber, M.Y. Nakai, R.D. Birkhoff: Adv. Radiat. Biology 3, 1 (1969)
5.38 B.L. Henke, J.A. Smith, D.T. Attwood: J. Appl. Phys. 48, 1852 (1977)
5.39 B.L. Henke, J. Liesegang, S.D. Smith: Phys. Rev. B 19, 3001 (1979)
5.40 G. Martens, P. Rabe, N. Schwentner, A. Werner: J. Phys. C 11, 3125 (1978)
5.41 A.P. Lukirskii, LA. Brytov: Sov. Phys.-Solid State 6, 33 (1964)
5.42 W. Gudat, e. Kunz: Phys. Rev. Lett. 29, 169 (1972)
5.43 G. Martens, P. Rabe, G. Tolkiehn, A. Werner: Phys. Status Solidi (a) 55, 105 (1979)
5.44 T.K. Sham, R.G. Carr: J. Chern. Phys. 83, 5914 (1985)
5.45 J. Stohr: In X-ray Absorption: Principles, Applications, Techniques of EX AFS, SEX AFS and
XANES, ed. by D.e. Koningsberger, R. Prins (Wiley, New York 1988) p. 443
5.46 B.L. Henke, J.P. Knauer, K. Premaratne: J. Appl. Phys. 52, 1509 (1981)
5.47 L.G. Eliseenko, V.N. Schemelev, M.A. Rumsh: Sov. Phys.-Tech. Phys. 13, 122 (1968)
5.48 G.D. Mahan: Phys. Rev. B 2, 4334 (1970)
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5.49 R.S. Williams, P.S. Wehner, J. Stohr, D.A. Shirley: Surf. Sci. 75, 215 (1978)
5.50 e.S. Fadley: In Electron Spectroscopy: Theory, Techniques and Applications, Vol. 2, ed. by
e.R. Brundle, A.D. Baker (Academic, New York 1978) p. 1
5.51 C.N. Yang: Phys. Rev. 74, 764 (1948)
5.52 J.W. Gallagher, e.E. Brion, J.A.R. Samson, P.W. Langhoff: J. Phys. Chem. Ref. Data 17, 9
(1988)
5.53 R.F. Davis, S.D. Kevan, B.-e. Lu, J.G. Tobin, D.A. Shirley: Chem. Phys. Lett. 71, 448 (1980)
5.54 J.L. Wiza: Nucl. Instrum. Methods 162, 587 (1979). The characteristics of spiraltron, channel-
tron or channelplate electron multipliers are also discussed in technical data sheets available
from the manufacturers, e.g., in the USA, Galileo Electron-Optics Corp., Sturbridge, MA;
Hamamatsu Corp., Middlesex, NJ; or Varian Assoc., Palo Alto, CA
5.55 J.G. Timothy, R.P. Madden: In Handbook on Synchrotron Radiation, Vol. la, ed. by E.E. Koch
(North-Holland, Amsterdam 1983) p. 315
5.56 P.W. Palmberg: J. Electron Spectrosc. 5, 691 (1974). Also see data sheets of Perkin-Elmer,
Physical Electronics Division, Eden Prairie, MN, USA
5.57 N.V. Smith, S.D. Kevan: Nucl. Instrum. Methods 195, 309 (1982)
5.58 J.H. Hubbell, H.A. Gimm, I. Overbo: J. Phys. Chem. Ref. Data 9,1023 (1980)
5.59 K. Tohji, Y. Udagawa: Phys. Rev. B 39, 7590 (1989)
5.60 B.E. Warren: X-ray Diffraction (Addison-Wesley, Reading, MA 1969)
5.61 J.H. Hubbell, W.J. Veigele, E.A. Briggs, R.T. Brown, D.T. Cromer, R.J. Howerton: J. Phys.
Chem. Ref. Data 4, 471 (1975)
5.62 F. Stem: In Solid State Physics, Vol. 15, ed. by F. Seitz, D. Turnbull (Academic, New York
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5.63 O.S. Heavens: Optical Properties of Thin Solid Films (Dover, New York 1965)
5.64 P. Beckmann, A. Spizzichino: The Scattering of Electromagnetic Waves from Rough Surfaces
(Pergamon, New York 1963)
5.65 V. Rehn: Proc. SPIE 640, 106 (1986)
5.66 E.L. Church, J.M. Zavada: Appl. Opt. 14, 1788 (1975)
5.67 Mau Hsiung Chen: Private communication
5.68 J.B. Hastings: In EXAFS Spectroscopy Techniques and Applications: ed. by B.K. Teo,
D.C. Joy (Plenum, New York 1981) p. 171
5.69 S.M. Heald: In X-ray Absorption: Principles, Applications, Techniques of EXAFS, SEXAFS
and XANES, ed. by D.C. Koningsberger, R. Prins (Wiley, New York 1988) p. 119
5.70 H. Hogrefe: Ph.D. thesis, Universitiit Hamburg (1985); DESY-HASYLAB Report 85-{)5
(1985)
S.71 H. Hogrefe, C. Kunz: Appl. Opt. 26, 2851 (1987)
5,.72 V. Rehn, V.O. Jones, J.M. Elson, J.M. Bennett: Nucl. Instrum. Methods 172, 307 (1980)
5,73 D.A. Fischer, J. Colbert, J.L. Gland: Rev. Sci. Instrum. 60, 1596 (1989)
5i74 E.L. Church, H.A. Jenkinson, J.M. Zavada: Opt. Eng. 18, 125 (1979)
5.75 J.M. Elson, V. Rehn, J.M. Bennett, V.O. Jones: Proc. SPIE 315, 193 (1981)
5.76 J.A.R. Samson: Techniques of Vacuum Ultraviolet Spectroscopy (Wiley, New York 1967)
5.77 D.A. Fischer, U. Dobler, D. Arvanitis, L. Wenzel, K. Baberschke, J. Stohr: Surf. Sci. 177, 114
(1986)
5.78 J. Stohr, E.B. Kollin, D.A. Fischer, J.B. Hastings, F. Zaera, F. Sette: Phys. Rev. Lett. 55,1468
(1985)
5.79 D.A. Fischer, J.B. Hastings, F. Zaera, J. Stohr, F. Sette: Nucl. Instrum. Methods A246, 561
(1986)
5.80 D. Arvanitis, U. Dobler, L. Wenzel, K. Baberschke, J. Stohr: J. de Phys. Colloque C8, 173
(1986)
5.81 D.A. Fischer, J.L. Gland: Proc. SPIE 733, 504 (1986)
5.82 F. Zaera, D.A. Fischer, S. Shen, J.L. Gland: Surf. Sci. 194, 205 (1988)
5.83 K. Baberschke: Private communication
5.84 Absorption coefficients for various soft X-ray filters are listed in:
B.L. Henke, R.L. Elgin: In Advances in X-ray Analysis, Vol. 13, ed. by B.L. Henke,
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J.B. Newkirk, G.R. Mallett (Plenum, New York 1970) p. 639;

B.L. Henke, E.S. Ebisu: In Advances in X-Ray Analysis, Vol. 17, ed. by e.L. Grant,
e.S. Barrett, J.B. Newkirk, C.O. Ruud (Plenum, New York 1974) p. 150;
B.L. Henke, P.A. Jaanimagi: Rev. Sci. Instrum. 56, 1537 (1985)
5.85 B.L. Henke, M. Tester: In Advances in X-ray Analysis, Vol. 18, ed. by W.L. Pickles,
e.S. Barrett, J.B. Newkirk, e.O. Ruud (Plenum, New York 1975) p. 76
5.86 Sales brochure (1988) of KEVEX Corp., San Carlos, CA 94070, USA, on the "Quantum"
Si(Li) soft X-ray detector
5.87 J. Barth, E. Tegeler, M. Krisch, R. Wolf: Proc. SPIE 733, 481 (1986);
D. Seligson, L. Pan, P. King, P. Pianetta: Nucl. Instrum. Methods A266, 612 (1988)
5.88 J. Stohr, R. Jaeger, J. Feldhaus, S. Brennan, D. Norman, G. Apai: Appl. Opt. 19, 3911 (1980)
5.89 J. Stohr: J. Vac. Sci. Technol. 16, 37 (1979)
5.90 D.A. Outka, J. Stohr, W. Jark, P. Stevens, 1. Solomon, R.I. Madix: Phys. Rev. B 35, 4119
(1987)
5.91 D.A. Outka, J. Stohr, J.P. Rabe, J. Swalen: J. Chern. Phys. 88, 4076 (1988)
5.92 D.A. Fischer: Private communication
5.93 J.F. Morar, F.J. Himpsel, G. Hollinger, J.L. Jordan, G. Hughes, F.R. McFeely: Phys. Rev. B
33, 1346 (1986)
5.94 G. Comelli, J. Stohr: Surf. Sci. 200, 35 (1988)
5.95 G. Comelli, J. Stohr, W. Jark, B. Pate: Phys. Rev. B 37, 4383 (1988)
5.96 G. Comelli, J. Stohr, C.J. Robinson, W. Jark: Phys. Rev. B 38, 7511 (1988)

Chapter 6
6.1 R.T. Sanderson: Chemical Bonds and Bond Energy (Academic, New York 1971)
6.2 L. Pauling: The Nature of the Chemical Bond (Cornell University Press, Ithaca 1960)
6.3 S. Fahy, X.W. Wang, S. G. Louie: Phys. Rev. Lett. 61, 1631 (1988)
6.4 A. Cartner, B. Robinson, P.I. Gardner: J Chern. Soc., Chern. Commun. 317 (1973)
6.5 J.A. Connor: Topics Current Chern. 71, 71 (1979)
6.6 M. Calhorda, M. de C.T. Carrondo, A. Dias, A. Domingos, J. Simones, C. Teixeira:
Organomet. 5, 660 (1986)
6.7 G.N. Derry, P.N. Ross: J. Chern. Phys. 82, 2772 (1985)
6.8 M. Bowker, M.A. Barteau, R.I. Madix: Surf. Sci. 92, 528 (1980)
6.9 J.L. Gland, B.A. Sexton, G.A. Fisher: Surf. Sci. 95, 587 (1980)
6.10 T.H. Upton, P. Stevens, R.J. Madix: J. Chern. Phys. 88, 3988 (1988)
6.11 G. Ertl: In The Nature of the Surface Chemical Bond, ed. by T.N. Rhodin, G. Ertl (North-
Holland, Amsterdam 1979) p. 315
6.12 S.e. Fain, Jr., M.F. Toney, R.D. Diehl: In Proc 9th Int. Vacuum Congress and 5th Int. Can! on
Solid Surfaces, ed. by J.L. de Segovia (Imprenta Moderna, Madrid 1983) p. 129
6.13 A.e. Luntz, J. Grimblot, D.E. Fowler: Phys. Rev. B 39, 12903 (1989)
6.14 R.D. Etters, A.A. Helmy, K. Kobashi: Phys. Rev. B 28, 2166 (1983)
6.15 R.e. Weast (ed.): Handbook of Chemistry and Physics, 53rd edn. (CRC, Cleveland, OH 1972)
6.16 e. Kittel: Introduction to Solid State Physics (Wiley, New York 1968)
6.17 Spectra recorded by A.P. Hitchcock: Private communication
6.18 A.P. Hitchcock, e.E. Brion: 1. Electron Spectrosc. 18, 1 (1980)
6.19 E. Riihl, A.P. Hitchcock: J. Am. Chern. Soc. 111, 2614 (1989)
6.20 J.T. Roberts, A.e. Liu, C.M. Friend, J. Stohr: Unpublished
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Chapter 7
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7.50 J.L. Solomon, R.J. Madix, J. StohE J. Chern. Phys. 94, 4012 (1991)
7.51 Y. Ma, e.T. Chen, G. Meigs, K. Randall, F. Sette: Phys. Rev. A 44, 1848 (1991)
7.52 B. Gumhalter, K. Wandelt, Ph. Avouris: Phys. Rev. B 37, 8048 (1988)
7.53 M. Grunze, M. Golze, W. Hirschwald, H.-J. Freund. H. Pulm, U. Seip, M.e. Tsai, G. Ert!.
J. Kiippers: Phys. Rev. Lett. 53, 850 (1984)

Chapter 8
8.1 J.L. Dehmer, D. Dill, S. Wallace: Phys. Rev. Lett. 43, 1005 (1979)
8.2 A.E. Orel, T.N. Rescigno, B.V. McKoy, P.W. Langhoff: J. Chern. Phys. 72,1265 (1980)
8.3 P.W. Langhoff, T.N. Rescigno, N. Padial, G. Csanak, B.V. McKoy: I. Chim. Phys. 77, 589
(1980)
8.4 T. Gustafsson, H.I. Levinson: Chern. Phys. Lett. 78, 28 (1981)
8.5 A.P. Hitchcock, e.E. Brion: I. Phys. B 14,4399 (1981)
8.6 e.R. Natoli: In EXAFS and Near Edge Structure. ed. by A. Bianconi, L. Incoccia, S. Stipcich,
Springer Ser. Chern. Phys. Vol. 27 (Springer, Berlin, Heidelberg 1983) p. 43
8.7 A. Bianconi, M. Dell'Ariccia, A. Gargano, e.R. Natoli: In EXAFS and Near Edge Structure, ed.
by A. Bianconi, L. Incoccia, S. Stipcich, Springer Ser. Chern. Phys., Vol. 27, (Springer, Berlin,
Heidelberg York 1983) p. 57
8.8 J. Stohr, J.L. Gland, W. Eberhardt, D. Outka, R.J. Madix, F. Sette, R.J. Koestner, U. Dobler:
Phys. Rev. Lett. 51, 2414 (1983)
8.9 F. Sette, J. Stohr, A.P. Hitchcock: J. Chern. Phys. 81, 4906 (1984)
8.10 F. Sette, J. Stohr, A.P. Hitchcock: Chern. Phys. Lett. 110, 517 (1984)
8.11 F. Sette, J. Stohr: In EXAFS and Near Edge Structure III, ed. by K.O. Hodgson, B. Hedman,
J.E. Penner-Hahn, Springer Proc. Phys., Vol. 2 (Springer, Berlin, Heidelberg 1984) p. 250
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8.12 A.P. Hitchcock, S. Beaulieu, T. Steel, J. Stohr, F. Sette: J. Chem. Phys. 80, 3927 (1984)
8.13 J. Stohr, F. Sette, A.L. Johnson: Phys. Rev. Lett. 53, 1684 (1984)
8.14 M.N. Piancastelli, D.W. Lindle, T.A. Ferrett, D.A. Shirley: J. Chem. Phys. 86, 2765 (1987)
8.15 M.N. Piancastelli, D.W. Lindle, T.A. Ferrett, D.A. Shirley: J. Chem. Phys. 87, 3255 (1987)
8.16 A.P. Hitchcock, J. Stohr: J. Chem. Phys. 87, 3253 (1987)
8.17 J.A. Sheehy, T.J. Gil, c.L. Winstead, R.E. Farren, P.W. Langhoff: J. Chem. Phys. 91, 1796
(1989)
8.18 J. Stohr, K.R. BauchspieB: Phys. Rev. Lett. 67, 3376 (1991)
8.19 BX Yang, J. Kirz, T.K. Sham: Phys. Lett. A 110, 301 (1985)
8.20 X. Yang, J. Kirz, T.K. Sham: J. de Phys. Colloq, 47, C8-585 (1986)
8.21 B.K. Teo, P.A. Lee: J. Am. Chem. Soc. 101, 2815 (1978)
8.22 A.G. McKale, B.W. Veal, A.P. Paulikas, S.-K. Chan, G.S. Knapp: J. Am. Chem. Soc. 110,3763
(1988)
8.23 B.X. Yang, J. Kirz, T.K. Sham: Phys. Rev. A. 36, 4298 (1987)
8.24 J.J. Rehr, R.C. Albers, J. Mustre de Leon: Physica B 158,417 (1989)
8.25 J.J. Rehr, J. Mustre de Leon, S.1. Zabinsky, R.C. Albers: J. Am. Chem. Soc. 113, 5135 (1991);
J. Mustre de Leon, J.J. Rehr, S.1. Zabinsky, R.C. Albers: Phys. Rev. B 44, 4146 (1991)
8.26 L.1. Schiff: Quantum Mechanics, 3rd edn. (McGraw-Hill, New York 1968) Sect. 9
8.27 A.P. Hitchcock: Phys. Scr. T3l, 159 (1990)
8.28 I. Ishii, A.P. Hitchcock: Private communication
8.29 E. Riihl, A.P. Hitchcock: Chem. Phys. 154, 323 (1991)
8.30 D. Arvanitis, U. Dobler, L. Wenzel, K. Baberschke, J. Stohr: Surf. Sci. 178,686 (1986)
8.31 J. Marsden, L.S. Bartell, P. Diodati: J. Mol. Struct. 39, 253 (1977)
8.32 I. Ishii, R. McLaren, A.P. Hitchcock, M.B. Robin: J. Chem. Phys. 87, 4344 (1987)
8.33 A.P. Hitchcock, C.E. Brion: J. Electron Spectrosc. 13, 193 (1978)
8.34 A.P. Hitchcock, M. Tronc: Chem. Phys. 121, 265 (1988)
8.35 F.W. Lytle, R.B. Greegor, AJ. Panson: Phys. Rev. B 37, 1550 (1988)
8.36 M. Kasrai, M.E. Fleet, T.K. Sham, G.M. Bancroft, K.H. Tan, J.R. Brown: Solid State Commun.
68, 507 (1988)
8.37 Structure Data of Free Polyatomic Molecules, Group 2, Vol. 7 of Landolt-Bomstein: Numerical
Data and Functional Relationships in Science and Technology (Springer, Berlin, Heidelberg
1976)
8.38 A.P. Hitchcock, I. Ishii: J. Electron Spectrosc. 42, 11 (1987)
8.39 A.P. Hitchcock: Private communication
8.40 R.N.S. Sodhi, C.E. Brion: J. Electron Spectrosc. 37, 1 (1985)
8.41 J.A. Horsley, J. Stohr, A.P. Hitchcock, D.C. Newbury, A.L. Johnson, F. Sette: J. Chern. Phys.
83, 6099 (1985)
8.42 I. Ishii, A.P. Hitchcock: J. Chem. Phys. 87, 830 (1987)
8.43 I. Ishii, A.P. Hitchcock: J. Electron Spectrosc. 46, 55 (1988)
8.44 G.R. Wight, C.E. Brion: J. Electron Spectrosc. 3, 191 (1974)
8.45 D.M. Barrus, R.L. Blake, AJ. Burek, K.C. Chambers, A.L. Pregenzer: Phys. Rev. A 20, 1045
(1979)
8.46 W.L. Jolly, K.D. Bomben, C.J. Eyermann: At. Data Nucl. Data Tables 31, 433 (1984); an update
is available from W.L. Jolly upon request
8.47 L.E. Sutton (Ed.): Tables of Interatomic Distances and Corifigurations in Molecules and Ions,
Special Publications Nos. 11 and 18 (Chemical Society, London 1958, 1965)
8.48 MJ.S. Dewar: Hyperconjugation (Ronald, New York 1962)
8.49 L. Pauling, H.S. Springall, K.J. Palmer: J. Am. Chem. Soc. 61, 927 (1939)
8.50 R.S. Mulliken: J. Chem. Phys. 7, 339 (1939)
8.51 R.S. Mulliken, C.A. Rieke, W.G Brown: J. Am. Chem. Soc. 63, 41 (1941)
8.52 W.L. Jorgensen, L. Salem: The Organic Chemist's Book of Orbitals (Academic, New York 1973)
8.53 A.D. Walsh: Trans. Faraday Soc. 42, 56 (1946); ibid 43,60,158 (1947); Discuss. Faraday Soc. 2,
18 (1947); J. Chem. Soc. 398 (1948)
8.54 C.A. Coulson: Proc. R. Soc. London A 207, 91 (1951)
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8.55 R. McLaren, S.A.C. Clark, I. Ishii, A.P. Hitchcock: Phys. Rev. A 36, 1683 (1987)
8.56 Spectra recorded by A.P. Hitchcock: Private communication
8.57 A.P. Hitchcock, D.e. Newbury, I. Ishii, J. Stohr, J.A. Horsley, R.D. Redwing, A.L. Johnson,
F. Sette: J. Chem. Phys. 85, 4849 (1986)
8.58 R.N.S. Sodhi, C.E. Brion: J. Electron Spectrosc. 37, 1 (1985)
8.59 W.H.E. Schwarz, T.e. Chang, U. Seeger, K.H. Hwang: Chem. Phys. 117,73 (1987)
8.60 A.e. Liu, J. Stohr, C.M. Friend, R.I. Madix: Surf. Sci. 235, 107 (1990)
8.61 W. Wurth, J. Stohr: Unpublished results
8.62 W. Wurth, J. Stohr: Vacuum 41, 237 (1990); and unpublished results
8.63 A.P. Hitchcock, e.E. Brion: J. Electron Spectrosc. 18, 1 (1980)
8.64 K. Siegbahn, C. Nordling, G. Johansson, J. Hedman, P.F. Heden, K. Hamrin, U. Gelius,
T. Bergmark, L.O. Werme, R. Manne, Y. Baer: ESCA Applied to Free Molecules (North-
Holland, Amsterdam 1969)
8.65 T.A. Carlson: Photoelectron and Auger Spectroscopy (Plenum, New York 1975)
8.66 C.R. Brundle: In Electronic Structure and Reactivity of Metal Surfaces, ed. by E.G. Derouane,
A.A. Lucas (Plenum, New York 1976) p. 389
8.67 e.S. Fadley: In Electron Spectroscopy: Theory, Techniques and Applications, Vol. 2, ed. by
e.R. Brundle, A.D. Baker (Academic, New York 1978) p. 1
8.68 M.B. Robin, I. Ishii, R. McLaren, A.P. Hitchcock: J. Electron Spectrosc. 47, 53 (1988)
8.69 E.W. Plummer, W.R. Salanek, J.S. Miller: Phys. Rev. B 18, 1673 (1978)
8.70 H.-J. Freund, E.W. Plummer: Phys. Rev. B 23, 4859 (1981)
8.71 M.R. Churchill, K.N. Amoh, H.J. Wasserman: Inorg. Chem. 20, 1609 (1981)
8.72 J. Stohr, R. Jaeger: Phys. Rev. B 26, 4111 (1982)
8.73 Y. Jugnet, F.J. Himpse1, Ph. Avouris, E.E. Koch: Phys. Rev. Lett. 53, 198 (1984)
8.74 E. Riibl, A.P. Hitchcock: J. Am. Chem. Soc. 111,2614 (1989)
8.75 A.P. Hitchcock, A.T. Wen, E. Riihl: J. Electron Spectrosc. 51, 653 (1990)
8.76 J.L. Solomon, R.J. Madix, J. Stohr: J. Chem. Phys. 93, 8379 (1990)
8.77 J. Stohr, R.J. Madix: Unpublished results
8.78 D. Arvanitis, K. Baberschke, L. Wenzel, U. Dobler: Phys. Rev. Lett. 57, 3175 (1986)
8.79 D. Arvanitis, H. Rabus, L. Wenzel, K. Baberschke: Z. Phys. D 11, 219 (1989)
8.80 R.J. Koestner, J. Stohr, J.L. Gland, J.A. Horsley: Chem. Phys. Lett. 105, 332 (1984)
8.81 J. Stohr, D.A. Outka, K. Baberschke, D. Arvanitis, J.A. Horsley, Phys. Rev. B 36, 2967 (1987)
8.82 J.A. Horsley, J. Stohr, R.J. Koestner: J. Chem. Phys. 83, 3146 (1985)
8.83 P.A. Stevens, R.J. Madix, J. Stohr: Surf. Sci. 230, 1 (1990)
8.84 A.P. Hitchcock, C.E. Brion: J. Electron Spectrosc. 19,231 (1980)
8.85 R.W.G. Wyckoff: Crystal Structures, Vol. 5 (Interscience, New York 1966)
8.86 R.I. Madix, J.L. Solomon, J. Stohr: Surf. Sci. 197, L253 (1988)
8.87 R.J. Reeder (ed.): Carbonates: Mineralogy and Chemistry, Reviews in Mineralogy, Vol. 11
(Mineralogical Society of America, Washington, DC 1983)
8.88 J. Zemann: Fortschr. Mineral. 59, 95 (1981)
8.89 D. Arvanitis, L. Wenzel, K. Baberschke: Phys. Rev. Lett. 59, 2435 (1987)

Chapter 9
9.1 W.L. Jorgensen, L. Salem: The Organic Chemist's Book of Orbitals (Academic, New York
1973)
9.2 J.N. Murrell, S.F.A. Kettie, J.M. Tedder: The Chemical Bond (Wiley, New York 1985)
9.3 J.M. Tedder, A. Nechvatal: Pictorial Orbital Theory (Pitman, London 1985)
9.4 E. Hecht, A. Zajac: Optics (Addison-Wesley, Reading, MA 1974) Chap. 8
9.5 S. Krinsky, M.L. Perlman, R.E. Watson: In Handbook on Synchrotron Radiation, ed. by
E.E. Koch (North-Holland, Amsterdam 1983) Chap. 2
9.6 e. Kunz: In Synchrotron Radiation, Techniques and Applications, ed. by e. Kunz, Topics Curro
Phys., Vol. 10 (Springer, Berlin, Heidelberg 1979) Chap. 1
9.7 J.D. Jackson: Classical Electrodynamics (Wiley, New York 1962)
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9.9 J.W. Davenport: Phys. Rev. Lett. 36, 945 (1976)
9.10 E.W. Plummer, W. Eberhardt: Adv. Chern. Phys. 49, 533 (1982)
9.11 M. Van Hove, W. Weinberg, C.-M. Chan: Low-Energy Electron Diffraction, Springer Ser. Surf.
Sci., Vol. 6 (Springer, Berlin, Heidelberg 1986)
9.12 M.D. Crapper, e.E. Riley, D.P. Woodruff, A. Puschmann, I. Haase: Surf. Sci. 171, 1 (1986)
9.13 D.A. Outka, J. Stohr, W. Jark, P. Stevens, J. Solomon, R.I. Madix: Phys. Rev. B 35, 4119
(1987)
9.14 R.A. Rosenberg, P.I. Love, V. Rehn: Phys. Rev. B 33, 4034 (1986)
9.15 J. Stohr, K. Baberschke, R. Jaeger, T. Treichler, S. Brennan: Phys. Rev. Lett. 47, 381 (1981)

Chapter 10
10.1 J.P. Collman, L.S. Hegedus, I.R. Norton, R.G. Finke: Principles and Applications of
Organotransition Metal Chemistry (University Science Books, Mill Valley, CA 1987)
10.2 M.R. Albert, J.T. Yates, Jr.: The Surface Scientist's Guide to Organometallic Chemistry
(American Chemical Society, Washington, DC 1987)
10.3 J.L. Solomon, R.I. Madix, J. Stohr: J. Chern. Phys. 93, 8379 (1990)
10.4 G.A. Somorjai: Chemistry in Two Dimensions: Surfaces (Cornell University Press, Ithaca
1981)
10.5 Ref. [10.1], Chap. 12
10.6 For a review see: H.P. Bonzel: Surf. Sci. Rep. 8, 43 (1987)
10.7 I.L. Gland: In Chemistry and Physics of Solid Surfaces VII, ed. by V.R. Vanselow, R. Howe,
Springer Ser. Surf. Sci., Vol. 10 (Springer, Berlin, Heidelberg 1988 p. 221
10.8 G. Blyholder: J. Phys. Chern. 68, 2772 (1964);
G. Blyholder, M.e. Allen: J. Am. Chern. Soc. 91, 3158 (1969)
10.9 F. Sette, J. Stohr, E.B. Kollin, D.I. Dwyer, J.L. Gland, J.L. Robbins, A.L. Johnson: Phys.. Rev.
Lett. 54, 935 (1985)
10.10 E. Riihl, A.P. Hitchcock: J. Am. Chern. Soc. 111,2614 (1989);
A.P. Hitchcock, A.T. Wen, E. Riihl: J. Electron Spectrosc. 51, 653 (1990)
10.11 P. Chini: Inorg. Chim. Acta Rev. 2, 31 (1968)
10.12 D.H. Parker, D.A. Fischer, J. Colbert, B.E. Koel, J.L. Gland: Surf. Sci. 236, L372 (1990)
10.13 F. Zaera, D.A. Fischer, S. Shen, J.L. Gland: Surf. Sci. 194,205 (1988)
10.14 U. Hofer, P. Morgen, W. Wurth, E. Umbach: Phys. Rev. Lett. 55, 2979 (1985)
10.15 K.e. Prince, G. Paolucci, A.M. Bradshaw: Surf. Sci. 175, 101 (1986)
10.16 A.e. Luntz, J. Grimblot, D.E. Fowler: Phys. Rev. B 39, 12903 (1989)
10.17 M. Grunze, M. Golze, W. Hirschwald, H.-I. Freund. H. Pulm, U. Seip, M.e. Tsai, G. Ertl,
I. Kiippers: Phys. Rev. Lett. 53, 850 (1984)
10.18 W. Wurth, J. Stohr, P. Feulner, X. Pan, K.R. Bauchspie13, Y. Baba, E. Hudel, G. Rocker,
D. Menzel: Phys. Rev. Lett. 65, 2426 (1990)
10.19 J. Grimblot, A.e. Luntz, D.E. Fowler: J. Electron Spectrosc. 52, 161 (1990)
10.20 I.L. Gland, B.A. Sexton, G.B. Fisher: Surf. Sci. 95, 587 (1980)
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10.22 R.F.W. Bader, W.H. Henneker, P.E. Cade: J. Chern. Phys. 46, 3341 (1967)
10.23 W.L. Jorgensen, L. Salem: The Organic Chemist's Book of Orbitals (Academic, New York
1973)
10.24 I.A. Horsley, J. Stohr, R.I. Koestner: J. Chern. Phys. 83, 3146 (1985)
10.25 M. Zomack, K. Baberschke: Unpublished results;
M. Zomack: Ph.D. dissertation, Freie Universitiit Berlin (1987)
10.26 J. Korringa: Physica 16,601 (1950)
10.27 D.A. Outka, J. Stohr, W. Jark, P. Stevens, J. Solomon, R.I. Madix: Phys. Rev. B 35, 4119
(1987)
10.28 E. Riihl, A.P. Hitchcock: Chern. Phys. 154, 323 (1991)
10.29 Y. Ma, e.T. Chen, G. Meigs, K. Randall, F. Sette: Phys. Rev. A 44, 1848 (1991)
10.30 I. Ishii, R. McLaren, A.P. Hitchcock, M.B. Robin: J. Chern. Phys. 87, 4344 (1987)
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10.31 G.C. DeFotis: Phys. Rev. B 23, 4714 (1981)

10.32 A.E. Martell, D.T. Sawyer (eds.): Oxygen Complexes and Oxygen Activation by Transition
Metals (Plenum, New York 1988)
10.33 L. Vaska: Acc. Chern. Res. 11, 348 (1976)
10.34 M.B. Hall: In Ref. [10.32], p. 3
10.35 T.H. Upton, P. Stevens, R.J. Madix: J. Chern. Phys. 88, 3988 (1988)
10.36 J. Stohr: Unpublished results
10.37 A.G. Sharpe: Inorganic Chemistry (Longman, Harlow, UK and Wiley, New York 1986)
Chap. 4
10.38 PA Stevens: Ph.D. Dissertation, Stanford University (1988) (unpublished)
10.39 P.A. Stevens, T.H. Upton, J. Stohr, R.I. Madix: Phys. Rev. Lett. 67, 1653 (1991)
10.40 R.I. Koestner, J. Stohr, J.L. Gland, JA Horsley: Chern. Phys. Lett. 105, 332 (1984)
10.41 J. Somers, A.W. Robinson, Th. Lindner, D. Ricken, A.M. Bradshaw: Phys. Rev. B 40, 2053
(1989)
10.42 K.P. Huber, G. Herzberg: Molecular Spectra and Molecular Structure, IV. Constants of
Diatomic Molecules (Van Nostrand Reinhold, New York 1979)
10.43 M. Zeitz, S.D. Peyerimhoff, R.J. Buenker: Chern. Phys. Lett. 64, 243 (1979)
10.44 C. Petrongolo, P.J. Bruna, S.D. Peyerimhoff, R.J. Buenker: J. Chern. Pbys. 74,4594 (1981)
10.45 M. Zeitz, S.D. Peyerimhoff, R.J. Buenker: Chern. Phys. Lett. 58, 487-(1978)
10.46 M.A. Barteau, R.I. Madix: Surf. Sci. 115, 355 (1982)
10.47 M.B. Hugenschmidt, P. Dolle, J. Jupille, A. Cassuto: J. Vac. Sci. Technol. A 7, 3312 (1989)
10.48 H. Steininger, H. Ibach, S. Lehwald: Surf. Sci. 117, 685 (1982)
10.49 For a review, see H. Ibach, D.L. Mills: Electron Energy Loss Spectroscopy and Surface
Vibrations (Academic, New York 1982) p. 326
10.50 F. Zaera, D.A. Fischer, R.G. Carr, E.B. Kollin, J.L. Gland: Electrochemical Surface Science:
Molecular Phenomena at Electrode Surfaces, ed. by M.P. Soriaga, ACS Symposium Series
No. 378 (American Chemical Society, Washington, DC 1988) p. 131
10.51 A.F. Wells: Structural Inorganic Chemistry (Oxford University Press, Oxford 1975)
10.52 R.A. Love, T.F. Koetzle, G.J.B. Williams, L.C. Andrews, R. Bau: Inorg. Chern. 14, 2653
(1975)
10.53 Structure Data of Free Polyatomic Molecules, Group 2, Vol. 7 of Landolt-Bornstein:
Numerical Data and Functional Relationships in Science and Technology (Springer, Berlin,
Heidelberg 1976)
10.54 A.M. Bradshaw, J. Somers: Phys. Scr. T31, 189 (1990)
10.55 L. Pauling: The Nature of the Chemical Bond (Cornell University Press, Ithaca 1960)
10.56 A.L. Johnson, E.L. Muetterties, J. Stohr: J. Am. Chern. Soc. lOS, 7183 (1983)
10.57 J.A. Horsley, J. Stohr, A.P. Hitchcock, D.C. Newbury, A.L. Johnson, F. Sette: J. Chern. Phys.
83, 6099 (1985)
10.58 A.C. Liu, C.M. Friend: J. Chern. Phys. 89, 4396 (1988)
10.59 A.C. Liu, J. Stohr, C.M. Friend, R.I. Madix: Surf. Sci. 235, 107 (1990)
10.60 J.L. Solomon, R.J. Madix, J. Stohr: Surf. Sci. 255, 12 (1991)
10.61 M. Bader, 1. Haase, K.-H. Frank, C. Ocal, A. Puschmann: J. de Phys. Colloq. C8 47, 491
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10.62 E. Riihl, A.P. Hitchcock: 1. Am. Chern. Soc. 111, 5069 (1989)
10.63 H. Ohtani, M.A. Van Hove, G.A. Somorjai: In The Structure of Surfaces II, ed. by 1.F. van
der Veen, M.A. Van Hove, Springer Ser. Surf. Sci., Vol. 11 (Springer, Berlin, Heidelberg 1988)
p. 219
10.64 C.M. Friend, J.T. Roberts: Acc. Chern. Res. 21, 394 (1988)
10.65 J. Stohr, D.A. Outka: Phys. Rev. B 36, 7891 (1987)
10.66 A.C. Liu, C.M. Friend, J. Stohr: Surf. Sci. 236, L349 (1990)
10.67 J.G. Serafin, C.M. Friend: J. Am. Chern. Soc. 111, 4233 (1989)
10.68 J.G. Serafin, C.M. Friend: Surf. Sci. 209, L163 (1989)
10.69 J.T. Roberts, C.M. Friend: J. Chern. Phys. 88, 7172 (1988)
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Organomet. 5, 660 (1986)
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10.76 D.A. McKeown, G.A. Waychunas, G.E. Brown, Jr.: J. Non-Cryst. Solids 74, 325 (1985)
10.77 D.A. McKeown, G.A. Waychunas, G.E. Brown, Jr.: J. Non-Cryst. Solids 74, 349 (1985)
10.78 J. Wong, C.L. Spiro, D.H. Maylotte, F.W. Lytle, R.B. Greegor: In EXAFS and Near Edge
Structure Ill, ed. by K.O. Hodgson, B. Hedman, J.E. Penner-Hahn, Springer Proc. Phys.,
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Vol. 1, p. 223 and Vol. 4, p. 203;
R.R. Chianelli: Catal. Rev.-Sci. Eng. 26, 361 (1984)
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10.82 e.B. Duke: J. Vac. Sci. Technol. A 3, 732 (1985)
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10.85 G. Tourillon, E. Dartyge, A. Fontaine, R. Garrett, M. Sagurton, P. Xu, G.P. Williams:
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10.86 J.A. Horsley: In Chemistry and Physics of Solid Surfaces VII, ed. by V.R. Vanselow,
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10.87 A.P. Hitchcock, J.A. Horsley, J. Stohr: J. Chern. Phys. 85, 4835 (1986)
10.88 For a tabulation ofISEELS spectra see: A.P. Hitchcock: J. Electron Spectrosc. 25, 245 (1982).
An update is available from the author upon request
10.89 Ref. [10.1], Chap. 9
10.90 T. Chivers, P.L. Timms: J. Organomet. Chern. 118, C37 (1976)
10.91 A.L. Johnson: Ph.D. Dissertation, University of California, Berkeley (1986) (unpublished)
10.92 J. Stohr, E.B. Kollin, D.A. Fischer, J.B. Hastings, F. Zaera, F. Sette: Phys. Rev. Lett. 55,1468
(1985)
10.93 J.T. Roberts, e.M. Friend: Surf. Sci. 186, 201 (1987)
10.94 S. McLaughlin: Annu. Rev. Biophys. Chern. 18, 113 (1989)
10.95 L. Stryer: Biochemistry (Freeman; New York 1988)
10.96 K.B. Blodgett, I. Langmuir: Phys. Rev. 51, 964 (1937)
10.97 G.L. Gaines, Jr.: Insoluble Monolayers at Liquid-Gas Interfaces (Wiley-Interscience,
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10.98 E. von Sydow: Arkiv fOr Kemi 9, 231 (1955)
10.99 See: Thin Solid Films 132-134 (1985)
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10.101 J.P. Rabe, J.D. Swalen, J.F. Rabolt: J. Chern. Phys. 86, 1601 (1987)
10.102 K. Seki, N. Ueno, U.O. Karlsson, R. Engelhardt, E.E. Koch: Chern. Phys. 105, 247 (1986)
10.103 S. Garoff, H.W. Deckman, J.H. Dunsmuir, M.S. Alvarez. J.M. Bloch: J. de Phys. 47, 701
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10.104 M. Pomerantz, A. Segmiiller: Thin Solid Films 68,33 (1980)
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10.109 DA Outka, J. Stohr. J.P. Rabe, J. Swalen: J. Chern. Phys. 88, 4076 (1988)
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Chapter 11
11.1 H. Petersen: Opt. Commun. 40, 402 (1982); Nuc1. Instrum. Methods A 246, 260 (1986)
11.2 M. Domke, A. Puschmann, e. Xue, D.A. Shirley, G. Kaindl, H. Petersen: Synchrotron Rad.
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11.3 e.T. Chen, E.W. Plummer, M.R. Howells: Nuc1. Instrum. Methods 222,103 (1984)
11.4 F. Sette, e.T. Chen: Rev. Sci. Instrum. 60, 1616 (1989);
e.T. Chen and F. Sette: Phys. Scr. T31, 119 (1990)
11.5 D. Attwood: Nuc1. Instrum. Methods A 291, 1 (1990)
11.6 A. Jackson: Synchrotron Rad. News 3,13 (1990)
11.7 B.P. Tonner: Synchrotron Rad. News 4, 20 (1991)
11.8 P.L. King, A. Borg, e. Kim, P. Pianetta, I. Lindau, G. Knapp, M. Keenlyside: Phys. Scr. 41,
413 (1990);
P.L. King, A. Borg, e. Kim, P. Pianetta, I. Lindau: Nuc!. Instrum. Methods A 291, 19 (1990)
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B.P. Tonner, G.R. Harp: J. Vac. Sci. Techno!. A 7, 1 (1989);
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11.11 KJ. Kim: Nuc1. Instrum. Methods 219, 425 (1984)
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11.13 P. Elleaume: Nucl. Instrum. Methods A 291, 371 (1990)
11.14 S. McLaughlin: Annu. Rev. Biophys. Chern. 18, 113 (1989)
11.15 M. Bader, J. Haase, K.-H. Frank, A. Puschmann, A. Otto: Phys. Rev. Lett. 56, 1921 (1986)
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11.20 Advanced Light Source Handbook, Lawrence Berkeley Laboratory, University of
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11.25 W. Eberhardt, J. Stohr, J. Feldhaus, E.W. Plummer, F. Sette: Phys. Rev. Lett. 51, 2370 (1983)
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11.28 L.J. Terminello, D.K. Shuh, FJ. Himpsel, D.A. Lapiano-Smith, J. Stohr, D.S. Bethune,
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11.29 R.F. Curl, R.E. Smalley: Science 242,1017 (1988);

H. Kroto: Science 242, 1139 (1988)
11.30 D.S. Bethune, G. Meijer, W.e. Tang, H.J. Rosen: Chern. Phys. Lett. 174,219 (1990)
11.31 A.P. Hitchcock, P. Fischer, A. Gedanken, M.B. Robin: J. Am. Chern. Soc. 91, 531 (1987)
11.32 J. Nordgren, R. Nyholm: Nucl. Instrum. Methods A 246, 242 (1986)
11.33 T.A. Callcott, K.L. Tsang, C.H. Zhang, D.L. Ederer, E.T. Arakawa: Rev. Sci. Instrum. 57,
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11.34 J. Nordgren, N. Wassdahl: Phys. Scr. T31, 103 (1990)
11.35 G. Wiech: In Inner-Shell and X-Ray Physics of Atoms and Solids, ed. by D.J. Fabian,
H. Kleinpoppen, L.M. Watson (Plenum, New York 1981) p. 815

Appendices
A.l L.1. Schiff: Quantum Mechanics, 3rd edn. (McGraw-Hill, New York 1968) Sect. 14
A.2 Ref. [A.1], Sect. 15
A.3 Ref. [A.1], Sect. 19
A.4 B.K. Teo, P.A. Lee: J. Am. Chern. Soc. 101,2815 (1978)
A.5 J.E. Muller, W.L. Schaich: Phys. Rev. B 27, 6489 (1983)
A.6 J.J. Barton, D.A. Shirley: Phys. Rev. B 32, 1906 (1985)
A.7 J.J. Rehr. R.e. Albers: Phys. Rev. B 41, 8139 (1990)
A.8 Ref. [A.l], Sects. 18 and 19
A.9 P.A. Lee, G. Beni: Phys. Rev. B 15, 2862 (1977)
[Link] P.-O. Lowdin: Adv. Phys. 5, 1 (1956)
A.l1 J.J. Barton, e.e. Bahr, Z. Hussain, S.W. Robey, J.G. Tobin, L.E. Klebanoff, D.A. Shirley:
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A.l2 G.M. Rothberg, K.M. Choudhary, M.L. denBoer, G.P. Williams, M.H. Hecht, I. Lindau:
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A.13 P.A. Lee: Phys. Rev. B 13, 5261 (1976)
A.14 1.1. Barton, D.A. Shirley: Phys. Rev. B 32, 1892 (1985)
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B.1 1. Stohr. X. Pan, A. Liu, C.M. Friend: Unpublished (1992)
B.2 R. Jaeger, J. Stohr, T. Kendelewicz: Surf. Sci. 134, 547 (1983)
B.3 D. Strongin, J. Mowlem: Surf. Sci. 247, L209 (1991)
BA D. Coulman, A. Puschmann, W. Wurth, H.-P. Steinriick, D. Menzel: Chern. Phys. Lett. 148,
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B.5 R. McGrath, A.A. MacDowell, T. Hashizume, F. Sette, P.H. Citrin: Phys. Rev. B 40, 9457
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B.6 R. McGrath, A.A. MacDowell, T. Hashizume, F. Sette, P.H. Citrin: Phys. Rev. Lett. 64, 575
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B.7 P.A. Stevens: Ph.D. Dissertation, Stanford University (1988) (unpublished)
B.8 P. Stevens, T. Upton, J. Stohr, R.J. Madix: Phys. Rev. Lett. 67, 1653 (1991)
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B.11 R.G. Carr, T.K. Sham, W. Eberhardt: Chern. Phys. Lett. 113,63 (1985)
B.12 D. Arvanitis, U. Dobler, L. Wenzel, K. Baberschke, J. Stohr: Surf. Sci. 178,686 (1986)
B.13 D. Arvanitis, K. Baberschke, L. Wenzel, U. Dobler: Phys. Rev. Lett. 57, 3175 (1986)
B.14 H. Rabus, D. Arvanitis, M. Domke, K. Baberschke: J. Chern. Phys. 96,1560 (1992)
B.15 R.J. Koestner, 1. Stohr, J.L. Gland, 1. Horsley: Chern. Phys. Lett. lOS, 332 (1984)
B.16 J.A. Horsley, J. Stohr, R.J. Koestner: J. Chern. Phys. 83, 3146 (1985)
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B.l8 A. Cassuto, M. Mane, J. Jupille: Surf. Sci. 249, 8 (1991)
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B.19 H. Rabus, D. Arvanitis, M. Domke, A. Puschmann, L. Wenzel, G. Comelli, G. Kaindl,

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B.20 D. Arvanitis, J. Singh, H. Rabus. T. Lederer, K. Baberschke: Phys. Rev. B 45,1518 (1992)
B.2l F. Zaera, D.A. Fischer, R.G. Carr, J.L. Gland: J. Chern. Phys. 89, 5335 (1988)
B.22 J. Solomon, R.J. Madix, J. Stohr: J. Chern. Phys. 93, 8379 (1990)
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B.24 R.J. Madix, J. Stohr: Unpublished (1989)
B.25 D. Coulman, J. Solomon, R.J. Madix, J. Stohr: Surf. Sci. 257, 97 (1991)
B.26 G. Bredael, W.T. Tysoe, F. Zaera: Langmuir 5,899 (1989)
B.27 A.C. Liu: Ph.D. Dissertation, Harvard University (1989) (unpublished)
B.28 A.P. Hitchcock, D.C. Newbury, I. Ishii, J. Stohr, J.A. Horsley, R.D. Redwing, A.L. Johnson,
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B.29 A.L. Johnson, E.L. Muetterties, J. Stohr: J. Am. Chern. Soc. 105,7183 (1983)
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B.31 M. Bader, J. Haase, K.-H. Frank, C. Ocal, A. Puschmann: J. de Phys. Colloq. C8, 491 (1986)
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B.39 W. Huber, M. Weinelt, P. Zebisch, H.-P. Steinriick: Surf. Sci. 253, 72 (1991)
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B.42 M.E. Kordesch, Th. Lindner, J. Somers, W. Stenzel, H. Conrad, A.M. Bradshaw, G.P.
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B.43 P.A. Stevens, R.J. Madix, C.M. Friend: Surf. Sci. 205,187 (1988)
B.44 P.A. Stevens, R.J. Madix, J. Stohr: J. Chern. Phys. 91, 4338 (1989)
B.45 A. Neumann, H. Rabus, D. Arvanitis, T. Salom un, K. Christmann, K. Baberschke: Phys.
Rev. Lett., to be published
B.46 R. Dudde, M.L.M. Rocco, E.E. Koch, S. Bernstorff, W. Eberhardt: J. Chern. Phys. 91, 20
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B.47 A.L. Johnson, E.L. Muetterties, 1. Stohr, F. Sette, J. Phys. Chern. 89, 4071 (1985)
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B.56 J. Stohr, K. Baberschke, R. Jaeger, T. Treichler, S. Brennan: Phys. Rev. Lett. 47, 381 (1981)
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Subject Index

helix 1,2
IX - in saturated chain 190
Acceptor bond 166,292 - in saturated ring 190
Acetylene 59 Bond energy 162
Active electron 28, 95 Bond length 111
Adiabatic limit 30 - correlation with u resonance 239
Adsorbate domain 283 - in large molecules 256
Adsorbate sensitivity 114 - in simple molecules 111, 250
Adsorbate-substrate scattering 173 - Z-dependence 254
Advanced Light Source 345 Bonding shift 265, 298
Alkali metal 295 Bonds 56
Allene 262 - digonal 56
Ammonia 53 - localized 56, 58
Area density 116 - sp 60
Argon 12 - Sp2 60
Aromatic molecules 201 - Sp3 60
Aromatic rings 199 - tetrahedral 56
Atomic adsorbate 172 - trigonal 56
Atomic scattering factor 134 Born approximation 81
Auger electron yield (AEY) detection 120 Born-Oppenheimer approximation 15
Auger lifetime 14 Bound state 30
Auger process 116 - transition 11, 21
Auger yield 116 Brightness 342
Broken symmetry 36
Backbonding 165,294 Buckminsterfullerene 347
Background correction 154 Building block principle 179,185
Backscattering 349
- amplitude 355 C-H resonance 92
- factor 355 C 60 347
Barn 8 Cadmium arachidate 334
Basis set 20 Calcium arachidate 334
- double-zeta 20 Canonical orbital 18
- minimal 20 Carbon dioxide 263
- triple-zeta 20 Carbon-metal bond 318
Battery box 131 Carbonate 275
Benzene 319 Carbonyl 165,298
Benzyne 327 Centrifugal barrier 85, 100
Bessel function 352 Centrifugal potential 38, 84
Binding energy 21 Chain tilt 341
Blyholder model 165, 296 Chain-like hydrocarbons 255
Bohr radius 10 Channeltron 130
Bond-bond interaction 185 Character table 52
- between Jr. orbitals 190 Chemical shift 107,265
- between u· orbitals 88, 111, 190 Chemisorbed molecule 164
394 Subject Index

Chemisorbed state 302 - X-ray 9

Chemisorption 292, 301 Dipole matrix element 10
Circular polarization 279 - angular dependence 69, 143,279
Classical electron radius 135 Dipole operator 11
Cluster ion 345 - acceleration form 11,39
CNDO 20 - length form 11
Coherent scattering 133 - velocity form 11
Compton scattering 134 Dipole selection rule 69, 72
Configuration interaction 27 Di-sigma bond 271, 315
Conjugation 61, 185 Displacement process 301
- in n systems 69, 185, 193 DNA 1
- in (J systems 69, 193 Domain 283
Continuum cross section 11, 97 Donor bond 165,292
Continuum state 21, 30 Double bond 61
Continuum step 225 Double-core-vacancy 97
Core hole localization 205
Core hole 26 Edge jump 212
- delocalized 26 Edge jump ratio 134
- localized 26, 205 Eigenchannel wavefunction 37, 101
Correlation energy 16, 22 Elastic scattering 133
Coulomb cusp 246 - angular dependence 143
Coulomb integral 19 Electric field vector 9, 278
Coulomb operator 18 Electron escape depth 123, 125
Coulomb potential 35 Electron lifetime 13
Cross section 132 Electron mean free path 123, 357
- coherent 133 Electron multiplier 130
- incoherent 133 Electron refraction 128
- photoelectric 133 Electron yield 118
Curve fitting 211 - Auger yield 119
CycIoalkane 259 - partial yield 119
Cylindrical mirror analyzer (CMA) 130 - total yield 119
Cylindrical potential 247 Electron-energy-Ioss spectroscopy 298, 315
Electron-hole interaction 207
~SCF 21 Electron-pair bond 56
Dangling bond 293 Elliptical polarization 278
Degree of linear polarization 279 Emittance 342
Delocalization 61, 185 Empty orbital 30
Density functional theory 34 Energy density 10
Depolarization term 46 Energy reference 250
Desulfurization 332 Equivalent cores approximation 22
Detectors 147 Equivalent orbital 58
- CMA 130 Erect field spectrograph 345
- gas proportional counter 130, 145 Error function 224
- partial electron yield 132 Ethane 59
- semiconductor diode 147 Ethylene 59
- Si(Li) 145 EXAFS 4
Diamond 5, 203, 229 - equation 44, 357
Diatomic molecule 49 - maxima 254
Di-carbon 309 Exchange integral 19
Difference spectrum 212,290 Exchange operator 18
Diffuse function 20 Exchange potential 34
Diffuse scattering 137, 138 - Hara 35
Dipole approximation 9, 278 - Hedin-Lundqvist 35
- ISEELS 81 - XIX 34
 Subject Index 395

Exchange splitting 78, 104,305 Helium 12

Excitation 4, 29 Hemoglobin 1, 2
Exciton 229 Herzberg-Teller vibronic coupling 92
Expansion theorem 356 High-Z atom 252
Extra-molecular interaction 162 Higher harmonics 155
Extra-molecular scattering 178 Hole lifetime 13
HOMO 52
fnumber 11 Huckel energy 65
[sum rule 12,86 Huckel theory 61
Fatty acid 334 Hund's rule 78
Fermi level 119,269 Hybrid orbital 56
Fermi level step 231 Hybridization 56
Fermi's Golden Rule 8 Hydrocarbons 102
Feshback-Fano method 42 Hydrodesulfurization 330
Final-state-relaxation shift 265 Hydrogen fluoride 53
Fine structure constant 10 Hyperconjugation 179, 256
Fingerprint method 329
First order perturbation 62 Improved virtual orbital 30
Fischer-Tropsch synthesis 295 Incoherent scattering 134
Fluorescence lifetime 14 - cross section 13 3
Fluorescence yield 116,117,133,135 Incoming wave 353
Fluorination 108 Index of refraction 281
Fock operator 18 Inelastic scattering 134
Formate 273 Inelastic tail 122, 125
Forward scattering in ISEELS 82 Initial-state-bonding shift 265
Fourier transform mass spectrometry 346 Inner potential 36, 38
Franck-Condon factor 17, 28 Insertion device 342
Franck-Condon principle 15, 17 Interaction energy 58, 59, 62
Free-electron wavefunction 10 Inter-molecular bond 318
Frenkel exciton 206 Intra-molecular scattering 178
Fresnel reflectivity 138 Inversion symmetry 49
Frontier orbital 165 Ion cyclotron resonance 346
Ion yield 117,118
g (gerade) 49 Ionization potential 11, 21
Gaussian 20, 213 Irreducible representation 49,72
- asymmetric peak Iineshape 214 - direct product 72
- peak Iineshape 213 ISEELS 4
- step lineshape 223 - technique 79
Gaussian disorder 357
Gaussian orbital 20 K-matrix 37, 242
Giant resonance 94 K-shell 4
- Iineshape 219 Kekule von Stradonitz 317
Gradient operator 10 Koopmans'Theorem 21
Graphite 5, 203, 289 Kossel structure 4
Group theory 49, 72 Kronig structure 4

Haber-Bosch process 3 L-edge 331

Hankel function 353 L2 eigenfunction 40
Hara exchange 35 Langmuir-Blodgett film 334
Harmonic oscillator 16 Laser plasma source 344
Hartree-Fock equations 17 Lateral interactions 294
- canonic form 18 Latter tail 35
Hartree-Fock method 15 LCAO method 19, 48, 49
Hedin-Lundqvist exchange 35 LCBO method 67
396 Subject Index

LEED - for nitric oxide 42

Lifetime width 12, 14 - for nitrogen 32, 49
Linear momentum operator 9 - for nitrogen dioxide 74
Linear polarization 279 - nonbonding 54
Lipid 334 - for phenol 202
Liquid surface 343 - for propane 68
Lone pair orbital 165 - for pyridine 327
- bond 293 - for triatomics 75
Lorentzian 12,213 - for water 54,91
- asymmetric peak lineshape 214 Molecular orientation 169
- peak lineshape 213 Monochromator 115, 342
- step lineshape 223 - dragon 342
Low-Z molecule 3 - spherical grating 348
Lowdin IX-expansion 355 - SX-700 342
LUMO 52 - transmission structures 157
Monopole selection rule 28
Magic angle 284 Muffin-tin potential 35
Mahan cone 128 Muffin-tin well 245
Main peak 265 Muffin-tin zero 243, 244
Manne-Aberg sum rule 29 Multi-electron effects 95, 228, 236
Mass density 122 Multi-electron transition 27
Mean free path 45 Multiple scattering 34, 358
Mean-square vibrational amplitude 204 - method 43
Metal-oxygen bond 324 Multiplet structure 22
Metal-sulfur bond 324 Myoglobin 1, 2, 348
Metallacycle 333
Metallocene 320 Neumann function 352
Methane 53 Nitric oxide 41
Microchannel array 345 Normalization 33, 154
Micro-NEXAFS 342 - by division 158
MINDO 20 - by subtraction 160
Model system 273 Norman criterion 36
Molecular orbital 18, 32, 42, 49
- for acetylene 60 ODA 209
- for ammonia 54, 87, 91 One-center approximation 71
- for aniline 202 One-electron approximation 29
- antibonding 49, 50 One-electron transition 27
- for benzene 201 Optical orbital 31, 106
- bonding 49 Optical oscillator strength 11
- for butadiene 65, 68 Orbital 30, 50, 57
- for C 2 1Ag 6 314 - 1t 48
- for carbon dioxide 53 - (J 48
- for carbon monoxide 32, 49 - equivalent 57, 58
- for C2 H4 Pt 2 316 - hybrid 56, 57
- for cyclobutane 194 - localized 56, 58
- for cyclopropane 194 - 2p 50
- for diatomics 50 - 2s 50
- for ethane 60 - symmetry adapted 51
- for ethylene 60, 104 - valence 58
- for formate 198 Orbital contour 102
- for hydrazine 87 Orbital energy 22
- for hydrogen fluoride 54, 91 Orbital orientation 69
- for methane 54, 91 OrganometaJlics 164
- for methyl radical 257 Oscillator strength 11
 Subject Index 397

Outgoing wave 353 - harmonic oscillator 16

Oxygen molecule 243 - inner 38
- molecular 85
n*-acceptor 293 - muffin-tin 35
n-aromatic molecule 194 - for N2 38,99
n-bond 49, 166,318 - for O 2 243
n-donor 293 - static exchange 31
n* resonance 88 - XIX 34
p-orbital 48 Potential barrier 84, 93
Packaging 3 Promoter 295
Paraffin 65, 66 Propene 183, 255
Pariser-Parr-Pople model 185 Proportional counter 145
Partial electron yield (PEY) detection 121 Propylene 255
Partial electron yield detector 132 Pseudo-diatomic 61
Partial wave scattering theory 353 Pseudo-spectrum 40
Particle-in-a-box 247 PVMK 209
Passive electron 28, 95 Pyridine 325
Peroxide 306, 308 Pyridyl 327
Phase shift 352
Phenoxide 322 Quadrupole transition 83
Phenyl ring 317 Quantum yield 126
Phenyl thiolate 322
Photoelectric cross section 133 Rayleigh scattering 133
Photoelectron diffraction 350, 357 Reactive-end bond 318
Photoelectron spectroscopy (PES) 21 Reference monitor 130
Photoelectron wavevector 352 Reflectivity 138
Photon mean free path 122 Relaxation energy 22
Physisorbed molecule 164 Relaxation shift 265
Physisorbed state 302 Resonance 83
Physisorption 267, 292, 301 - n* 83, 107, 185, 190
Plane orbital 277,281 - a* 88
Plane wave 354 - angular dependence 69, 279
PMDA 209 - Feshbach 93
PMMA 207 - multi-electron 95
PMPO 209 - shape 93
Polarization 70, 278 - valence/Rydberg 90
- circular 279 Resonance position 106
- elliptical 278 - n* 107
- linear 279 - a* 111
Polarization factor 279 - absolute 106, 264
Polarization function 20 - relative 106, 264
Poly-p-phenylenes 206 Restricted-Hartree-Fock method 31
Polyacenes 206 Ring expansion 322
Polyacetylene 230 Roothaan-Hall method 19
Polyenes 64, 66 Rotational splitting 16
Polyines 64 Rydberg orbital 21
Polypeptide chain 2 Rydberg resonance 90
Polystyrene 330 Rydberg transition 12
Poly thiophene 329 Rydberg states 85
Potential 30 Rydbergization 92
- atomic 15,85
- centrifugal 38, 85 a bond 49
- Coulomb 18, 35 a-conjugated molecule 260
- exchange 18, 34 a-donor 293
398 Subject Index

(1* resonance 93 - broken 72

- bond length correlation 239 - ground state 72
Saturated bond 59 Synchrotron radiation 115, 342, 343
Saturated ring 258 - second generation source 343
Scattered light 155 - third generation source 343
Scattering phaseshift 45
Schrodinger equation 16,352 Term value 107
Second order perturbation 62 Thiophene 329
Secular determinant 58 Thomas-Reiche-Kuhn sum rule 12
Self-consistent-field method 16 Thomson cross section 135
Self-energy 58, 62 Threefold symmetry 284
Semiconductor diode 147 Tilted-chain model 337
Semiempirical method 20 Time-resolved studies 344
SEXAFS 3 Total electron yield (TEY) detection 121
Shake-off 95 Total integrated scatter 139
Shake-up 95 Transition energy 20
Shape resonance 93 Transition matrix element 279
Si(Li) diode 145 Transition operator 22
Signal-to-background ratio 127, 150 Transition state method 22, 37, 100
Signal-to-noise ratio 150 Triple bond 61
Single bond 61 Twofold symmetry 283
Single scattering 349
Slater determinant 16 u (ungerade) 49
Slater integral 22 Uncertainty relation 14
Slater orbital 20 Undulator 342
Small atom approximation 353 - helical 343
sp hybrid 56 Universal curve 123
Sp2 hybrid 56
Sp3 hybrid 56 Vacuum level 119,269
Spectral moment 40 Vacuum level step 231
Spectral resolution 115 Valence bond theory 56
Spectrograph 344 Valence orbital 58
Spectromicroscopy 342 van-der-Waals bonding 162,267, 301
Specular reflectivity 138 Variation principle 16
Spherical harmonics 351 Vector orbital 277,280
Spin-dependent excitation 75 Vector potential 9
Spin-flip transition 76 Vibrational amplitude 94
Spin-orbital 16 Vibrational fine structure 80
Spin relaxation time 305 - for CO 80
Spiraltron 130 - for C 2 H 4 168
Square well potential 241, 245 - for N2 80, 87, 99
Standards for bond length determinations 273 Vibrational ground state 17
Stanford Synchrotron Radiation Vibrational levels 17
Laboratory IX Vibrational motions 14
Static exchange approximation 31,40 Virtual orbital 20
Step profile 222 Voigt profile 214
- arctan function 223 Volume density 122
- error function 224
StieJtjes-Tchebycheff method 39,311 Walsh diagram 74
Stieltjes-Tchebycheff orbital 41 Water molecule 53
Sudden approximation 28 Wavefunction normalization 10
Superoxide 304, 308 - bound state 33
Surface roughness 138 - continuum state 33
Symmetry 72 Well constant 246,248,249
 Subject Index 399

Well depth 248 - reflection 137

Wiggler 343 - scattering 133
Work function 119,269 - wave vector 9
- wavelength 9
Xcx multiple scattering method 34 XANES 4
XCX potential 34
X-ray 9 Yang's theorem 129
- absorption coefficient 82, 122
- absorption cross section 8, 133 Zeise's anion 315
- Raman spectroscopy 134 Zero overlap assumption 62
Listing of Illustrated K-Shell Spectra

Molecule Chemical State or Substrate Page

Acetonitrile gas 180, 217

Ag(llO) 180
solid 180
Acetylene gas 103,258
Ag(l00) 268
Allene gas 261
Ag(llO) 195
Allyl alcohol solid 181, 215
Ammonia gas 86,87,91
Aniline solid 202
Argon gas 12,96

Benzene gas 201, 261, 347

Ag(llO) 200,201,203,235,320
Mo(llO) 320
solid 5, 201, 202, 203
Benzyne Mo(llO) 328
Butadiene gas 186
Ag(llO) 186
solid 186
Butane gas 190
Butene gas 182

C 60 solid 347
Cadmium arachidate Si(l11) 192, 216, 335, 339
Calcium arachidate Si(lll) 335
Carbon dioxide gas 196,263
Carbon monoxide gas 89, 164, 227, 263
Mn 2 (CO).o 164
Mo(llO) 157, 164, 17l
Na/Pt(lll) 297
Ni(l00) 152, 159, 170
Pt(lll) 297
Carbonate Ag(110) 199,274
CdC0 3 274
Carbonyl difluoride gas 108
Cyc1o-butane gas 190,194,259
Cyc1o-hexane gas 190
Cyc1o-hexene gas 259
Cyc1o-octatetraene gas 259
402 Listing of Illustrated K -Shell Spectra

Molecule Chemical State or Substrate Page

Cyclo-pentane gas 190,259

Cyclo-pentene gas 259
Cyclo-propane gas 190, 194, 259

Diamond solid 5,203,229

Di-carbon Ag(110) 311
Dihydrofuran Ag(110) 235

Ethane gas 103, 110, 180, 190, 258

Cu(I00) 268
Ethylene gas 103, 109, 167, 168,215,226,
258,270
Ag(I00) 167, 168, 171, 195,270
Ag(llO) 200, 235, 268, 270
Cu(I00) 151, 167, 168,270
Pt(111) 270,316
solid 168

Fluoroethylenes gas 109

Fluoromethane gas 110,253
Formaldehyde gas 89, 108,273
Formate Ag(110) 198,273
Cu(I00) 176
Formic acid gas 208,273
Formyl fluoride gas 108

Graphite solid 5,203, 289

Helium gas 12
Hexadiyne solid 187
Hexane gas 190
Hydrazine gas 86,87
Hydrogen cyanide gas 180
Hydrogen fluoride gas 91
Hydrogen peroxide gas 308

Methane gas 91, 110

Methanol gas 89, 110,273
solid 181
Methoxide Cu(I00) 174
Methyl bromide gas 253
Methyl chloride gas 253
Methyl fluoride gas 253
Methyl iodide gas 253
Methylacetylene gas 187, 258
Ag(llO) 268
Methylformate gas 208
Monofluorobenzene gas 202
Monomethylamine gas 110

Neon gas 86
Nitrogen oxide Ni(I00) 170
 Listing of Illustrated K -Shell Spectra 403

Molecule Chemical State or Substrate Page

Nitrogen gas 86,87,98,215,222,227,237

Fe(lll) 237

Oxygen gas 105,236,308

Ag(llO) 161, 233, 306, 308
Pt(I11) 232, 236, 303, 308
Oxygen, atomic Cu(I00) 174

Pentane gas 190

Phenol solid 202
Phenoxide OjAg(llO) 323
OjMo(llO) 323
Phenylthiolate Mo(llO) 323
PMDA-MBCA PI solid 209
PMDA-ODA PI solid 209
PMMA solid 208
PMPO solid 209
Poly-3-methylthiophene Pt(I11) 332
Polyacetylene solid 230
Poly butadiene solid 182
Polyethylene solid 192
Polystyrene solid 230
Propane gas 190,261
Propanoic acid solid 188
Propanol solid 181
Propargyl alcohol solid 181, 188, 217
Propene gas 258,261
Ag(llO) 268
Propiolic acid solid 188, 189
PVMK solid 209
Pyridine gas 326
Ag(lll) 326
Pt(lll) 326
solid 326

Thiophene Pt(lll) 331,332

Water gas 91