DENSITY FUNCTIONAL

THEORY
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DENSITY FUNCTIONAL

A Practical Introduction

National Energy Technology Laboratory

Georgia Institute of Technology
THEORY

JANICE A. STECKEL
DAVID S. SHOLL
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Library of Congress Cataloging-in-Publication Data:

Sholl, David S.
Density functional theory : a practical introduction / David S. Sholl and Jan Steckel.
p. cm.
Includes index.
ISBN 978-0-470-37317-0 (cloth)
1. Density functionals. 2. Mathematical physics. 3. Quantum chemistry. I. Steckel, Jan.
II. Title.
QC20.7.D43S55 2009
530.140 4—dc22
2008038603

Printed in the United States of America

10 9 8 7 6 5 4 3 2 1
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CONTENTS

Preface xi

1 What Is Density Functional Theory? 1

1.1 How to Approach This Book, 1
1.2 Examples of DFT in Action, 2
1.2.1 Ammonia Synthesis by Heterogeneous Catalysis, 2
1.2.2 Embrittlement of Metals by Trace Impurities, 4
1.2.3 Materials Properties for Modeling Planetary Formation, 6
1.3 The Schrödinger Equation, 7
1.4 Density Functional Theory—From Wave Functions to Electron
Density, 10
1.5 Exchange –Correlation Functional, 14
1.6 The Quantum Chemistry Tourist, 16
1.6.1 Localized and Spatially Extended Functions, 16
1.6.2 Wave-Function-Based Methods, 18
1.6.3 Hartree – Fock Method, 19
1.6.4 Beyond Hartree –Fock, 23
1.7 What Can DFT Not Do?, 28
1.8 Density Functional Theory in Other Fields, 30
1.9 How to Approach This Book (Revisited), 30
References, 31
Further Reading, 32

v
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vi CONTENTS

2 DFT Calculations for Simple Solids 35

2.1 Periodic Structures, Supercells, and Lattice Parameters, 35
2.2 Face-Centered Cubic Materials, 39
2.3 Hexagonal Close-Packed Materials, 41
2.4 Crystal Structure Prediction, 43
2.5 Phase Transformations, 44
Exercises, 46
Further Reading, 47
Appendix Calculation Details, 47

3 Nuts and Bolts of DFT Calculations 49

3.1 Reciprocal Space and k Points, 50
3.1.1 Plane Waves and the Brillouin Zone, 50
3.1.2 Integrals in k Space, 53
3.1.3 Choosing k Points in the Brillouin Zone, 55
3.1.4 Metals—Special Cases in k Space, 59
3.1.5 Summary of k Space, 60
3.2 Energy Cutoffs, 61
3.2.1 Pseudopotentials, 63
3.3 Numerical Optimization, 65
3.3.1 Optimization in One Dimension, 65
3.3.2 Optimization in More than One Dimension, 69
3.3.3 What Do I Really Need to Know about Optimization?, 73
3.4 DFT Total Energies—An Iterative Optimization Problem, 73
3.5 Geometry Optimization, 75
3.5.1 Internal Degrees of Freedom, 75
3.5.2 Geometry Optimization with Constrained Atoms, 78
3.5.3 Optimizing Supercell Volume and Shape, 78
Exercises, 79
References, 80
Further Reading, 80
Appendix Calculation Details, 81

4 DFT Calculations for Surfaces of Solids 83

4.1 Importance of Surfaces, 83
4.2 Periodic Boundary Conditions and Slab Models, 84
4.3 Choosing k Points for Surface Calculations, 87
4.4 Classification of Surfaces by Miller Indices, 88
4.5 Surface Relaxation, 94
4.6 Calculation of Surface Energies, 96
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CONTENTS vii

4.7 Symmetric and Asymmetric Slab Models, 98

4.8 Surface Reconstruction, 100
4.9 Adsorbates on Surfaces, 103
4.9.1 Accuracy of Adsorption Energies, 106
4.10 Effects of Surface Coverage, 107
Exercises, 110
References, 111
Further Reading, 111
Appendix Calculation Details, 112

5 DFT Calculations of Vibrational Frequencies 113

5.1 Isolated Molecules, 114
5.2 Vibrations of a Collection of Atoms, 117
5.3 Molecules on Surfaces, 120
5.4 Zero-Point Energies, 122
5.5 Phonons and Delocalized Modes, 127
Exercises, 128
Reference, 128
Further Reading, 128
Appendix Calculation Details, 129

6 Calculating Rates of Chemical Processes Using

Transition State Theory 131
6.1 One-Dimensional Example, 132
6.2 Multidimensional Transition State Theory, 139
6.3 Finding Transition States, 142
6.3.1 Elastic Band Method, 144
6.3.2 Nudged Elastic Band Method, 145
6.3.3 Initializing NEB Calculations, 147
6.4 Finding the Right Transition States, 150
6.5 Connecting Individual Rates to Overall Dynamics, 153
6.6 Quantum Effects and Other Complications, 156
6.6.1 High Temperatures/Low Barriers, 156
6.6.2 Quantum Tunneling, 157
6.6.3 Zero-Point Energies, 157
Exercises, 158
Reference, 159
Further Reading, 159
Appendix Calculation Details, 160
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viii CONTENTS

7 Equilibrium Phase Diagrams from Ab Initio

Thermodynamics 163
7.1 Stability of Bulk Metal Oxides, 164
7.1.1 Examples Including Disorder—Configurational
Entropy, 169
7.2 Stability of Metal and Metal Oxide Surfaces, 172
7.3 Multiple Chemical Potentials and Coupled Chemical
Reactions, 174
Exercises, 175
References, 176
Further Reading, 176
Appendix Calculation Details, 177

8 Electronic Structure and Magnetic Properties 179

8.1 Electronic Density of States, 179
8.2 Local Density of States and Atomic Charges, 186
8.3 Magnetism, 188
Exercises, 190
Further Reading, 191
Appendix Calculation Details, 192

9 Ab Initio Molecular Dynamics 193

9.1 Classical Molecular Dynamics, 193
9.1.1 Molecular Dynamics with Constant
Energy, 193
9.1.2 Molecular Dynamics in the Canonical
Ensemble, 196
9.1.3 Practical Aspects of Classical Molecular
Dynamics, 197
9.2 Ab Initio Molecular Dynamics, 198
9.3 Applications of Ab Initio Molecular Dynamics, 201
9.3.1 Exploring Structurally Complex Materials:
Liquids and Amorphous Phases, 201
9.3.2 Exploring Complex Energy Surfaces, 204
Exercises, 207
Reference, 207
Further Reading, 207
Appendix Calculation Details, 208
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CONTENTS ix

10 Accuracy and Methods beyond “Standard” Calculations 209

10.1 How Accurate Are DFT Calculations?, 209
10.2 Choosing a Functional, 215
10.3 Examples of Physical Accuracy, 220
10.3.1 Benchmark Calculations for Molecular
Systems—Energy and Geometry, 220
10.3.2 Benchmark Calculations for Molecular
Systems—Vibrational Frequencies, 221
10.3.3 Crystal Structures and Cohesive Energies, 222
10.3.4 Adsorption Energies and Bond Strengths, 223
10.4 DFTþX Methods for Improved Treatment of Electron
Correlation, 224
10.4.1 Dispersion Interactions and DFT-D, 225
10.4.2 Self-Interaction Error, Strongly Correlated Electron
Systems, and DFTþU, 227
10.5 Larger System Sizes with Linear Scaling Methods and Classical
Force Fields, 229
10.6 Conclusion, 230
References, 231
Further Reading, 232

Index 235
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PREFACE

The application of density functional theory (DFT) calculations is rapidly

becoming a “standard tool” for diverse materials modeling problems in
physics, chemistry, materials science, and multiple branches of engineering.
Although a number of highly detailed books and articles on the theoretical
foundations of DFT are available, it remains difficult for a newcomer to
these methods to rapidly learn the tools that allow him or her to actually
perform calculations that are now routine in the fields listed above. This
book aims to fill this gap by guiding the reader through the applications of
DFT that might be considered the core of continually growing scientific litera-
ture based on these methods. Each chapter includes a series of exercises to give
readers experience with calculations of their own.
We have aimed to find a balance between brevity and detail that makes it
possible for readers to realistically plan to read the entire text. This balance
inevitably means certain technical details are explored in a limited way. Our
choices have been strongly influenced by our interactions over multiple
years with graduate students and postdocs in chemical engineering, physics,
chemistry, materials science, and mechanical engineering at Carnegie
Mellon University and the Georgia Institute of Technology. A list of Further
Reading is provided in each chapter to define appropriate entry points to
more detailed treatments of the area. These reading lists should be viewed
as identifying highlights in the literature, not as an effort to rigorously cite
all relevant work from the thousands of studies that exist on these topics.

xi
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xii PREFACE

One important choice we made to limit the scope of the book was to focus
solely on one DFT method suitable for solids and spatially extended materials,
namely plane-wave DFT. Although many of the foundations of plane-wave
DFT are also relevant to complementary approaches used in the chemistry
community for isolated molecules, there are enough differences in the appli-
cations of these two groups of methods that including both approaches
would only have been possible by significantly expanding the scope of the
book. Moreover, several resources already exist that give a practical “hands-
on” introduction to computational chemistry calculations for molecules.
Our use of DFT calculations in our own research and our writing of
this book has benefited greatly from interactions with numerous colleagues
over an extended period. We especially want to acknowledge J. Karl
Johnson (University of Pittsburgh), Aravind Asthagiri (University of
Florida), Dan Sorescu (National Energy Technology Laboratory), Cathy
Stampfl (University of Sydney), John Kitchin (Carnegie Mellon University),
and Duane Johnson (University of Illinois). We thank Jeong-Woo Han for
his help with a number of the figures. Bill Schneider (University of Notre
Dame), Ken Jordan (University of Pittsburgh), and Taku Watanabe
(Georgia Institute of Technology) gave detailed and helpful feedback on
draft versions. Any errors or inaccuracies in the text are, of course, our
responsibility alone.
DSS dedicates this book to his father and father-in-law, whose love of
science and curiosity about the world are an inspiration. JAS dedicates this
book to her husband, son, and daughter.

DAVID SHOLL

Georgia Institute of Technology,

Atlanta, GA, USA

JAN STECKEL

National Energy Technology Laboratory,

Pittsburgh, PA, USA