ELECTRON SPECTROSCOPY FOR ATOMS,

MOLECULES AND CONDENSED MATTER

Nobel lecture, 8 December, 1981

by
KAI SIEGBAHN
Institute of Physics, University of Uppsala, Sweden

In my thesis [1], which was presented in 1944, I described some work which I
had done to study β decay and internal conversion in radioactive decay by
means of two different principles. One of these was based on the semi-circular
focusing of electrons in a homogeneous magnetic field, while the other used a
big magnetic lens. The first principle could give good resolution but low
intensity, and the other just the reverse. I was then looking for a possibility of
combining the two good properties into one instrument. The idea was to shape
the previously homogeneous magnetic field in such a way that focusing should
occur in two directions, instead of only one as in the semi-circular case. It was
known that in betatrons the electrons performed oscillatory motions both in the
radial and in the axial directions. By putting the angles of period equal for the
two oscillations Nils Svartholm and I [2, 3] found a simple condition for the
magnetic field form required to give a real electron optical image i.e. we
established the two-directional or double focusing principle. It turned out that
the field should decrease radially as and that double focusing should occur

after π . simple mushroom magnet was designed, the circular

pole tips of which were machined and measured to fit the focusing condition.
ThB was deposited on a wire net and put into position in the pole gap. A
photographic plate was located at the appropriate angle and the magnet
current set to focus the strong F line of ThB on the plate. Already the first
experiment gave a most satisfactory result. Both the horizontal and the vertical
meshes of the wire net were sharply imaged on the plate. A more detailed
theory for the new focusing principle was worked out and a large instrument
with R = 50 cm was planned and constructed [4]. Due to the radially decreas-
ing field form an additional factor of two was gained in the dispersion, com-
pared to the homogeneous field form. Since all electrons, for reasonably small
solid angles, were returning to the symmetry plane of the field at the point of
focus no loss in intensity was experienced by increasing the radius of curvature
of the instrument. Very large dispersion instruments with good intensity and
much improved resolving power could therefore be designed to record β spectra
and internal conversion spectra from radioactive sources. The magnetic double
focusing was convenient for the fairly high energy electrons (50 keV-2 MeV)
64 Physics 1981

normally occurring in radioactive decay and the field form could easily be
achieved by means of shaping the poles of an iron magnet. In my laboratory
and in many other nuclear physics laboratories double focusing spectrometers
frequently became used for high resolution work [5]. This type of focusing was
also used subsequently by R. Hofstadter [6] in his well-known work on high
energy electron scattering from nuclei and nucleons.
During the late forties, the fifties and the early sixties I was much involved in
nuclear spectroscopy. This was a particularly interesting and rewarding time in
nuclear physics since the nuclear shell model, complemented with the collective
properties, was then developed, which to a large extent was founded on
experimental material brought together from nuclear decay studies. Nuclear
disintegration schemes were thoroughly investigated, and the spins and parities
of the various levels were determined, as well as the intensities and multipole
characters of the transitions. During this period the discovery of the non-
conservation of parity added to the general interest of the field. Also the form of
the interaction in β decay, appearing originally in Fermi’s theory, was exten-
sively investigated. A large part of my own and my students’ research was
therefore concerned with nuclear spectroscopy of radioactive decay [7-23]. In
1955 I edited a volume [24] on “Beta and Gamma Ray Spectroscopy”. In 1965
I concluded my own career as a nuclear spectroscopist by publishing [25]
“Alpha, Beta and Gamma Ray Spectroscopy”. In this extensive survey of
nuclear spectroscopy I had been able to collect the prodigious number of 77
coauthors, all being prominent authorities and in many cases the pioneers in
the various fields. Although my own scientific activity at that time had almost
entirely become directed towards the new field which is the subject of the
present article I have still kept my old interest in nuclear physics much alive as
the editor for the journal Nuclear Instruments and Methods in Physics Re-
search (NIM) ever since its start in 1957.
Let me now return to the situation around 1950. At that time my coworkers
and I had already for some time been exploring the high resolution field by
means of our large dispersion double focusing instrument and other methods,
such as the high transmission magnetic lens spectrometer and coincidence
techniques. Often I found, however, that my experimental work had to stop
and wait for radioactive samples, the reason being a capricious cyclotron. It
then came to my mind that I should try to simulate the radioactive radiation by
a substitute which I could master better than the cyclotron. I had found that a
very convenient way to accurately investigate gamma radiation from radioac-
tive sources was to cover them with a electron converter, i.e. a thin lead foil
which produced photoelectrons to be recorded in the spectrometer. I now
got the idea that I should instead use an X-ray tube to expel photoelectrons
from ordinary materials, in order to measure their binding energies to the
highest possible accuracy. In my nuclear physics work such binding energies
had to be added to the energy values of the internal conversion lines from the
radioactive sources in order to get the energies of the nuclear transitions. I
studied what had been done along these directions before [26, 27], and I finally
got a vague feeling that I could possibly make an interesting and perhaps big
 K. M. Siegbahn 65

step forward in this field if I applied the experience I had from nuclear
spectroscopy using the above mentioned external photoeffect and my high
resolution instruments. The previous investigations had confirmed that the
atomic electrons were grouped in shells, and by measuring on the photographic
plates the high energy sides of the extended veils from the various electron
distributions approximate values of the binding energies could be deduced. On
the other hand, since the observed electron distributions had no line structure
and consequently did not correspond to atomic properties, the attained preci-
sion and the actual information was far inferior to what could be obtained by
X-ray emission and absorption spectroscopy. I realized that electron spectros-
copy for atoms and solids could never become competitive with X-ray emission
or absorption spectroscopy unless I was able to achieve such a high resolution
that really well-defined electron lines were obtained with linewidths equal to or
close to the inherent atomic levels themselves.
I thought of these problems considerably and started to make plans for a new
equipment which should fulfill he highest demands on resolution at the low
electron energies I had to be concerned with, ten to a hundred times smaller
than in radioactive work. I recall I sat down for some days early in 1950 to try
to make a thorough calculation about the expected intensities. I designed [28,
29, 30] an ironfree double focusing spectrometer with R = 30 cm, in which I
should be able to measure the current with a precision of better than 1 part in
10 4. The spectrometer was surrounded by a big, three-component Helmholtz
coil system to eliminate, to better than 1 part in 10 3, the earth’s magnetic field
over the entire region of the spectrometer. If I had an X-ray tube with a Ka
radiation in the region of 5 keV, this would enable me to measure expelled
photoelectrons with a precision of a fraction of an electron volt. This I thought
was about sufficient in atomic physics. I also hoped to observe phenomena of
chemical interest provided I could realize the resolution I aimed at, but at that
time my ideas in this latter respect were of course very vague, centering around
atomic level shifts in alloys, etc. When I calculated the expected intensities of
the photoelectron lines, I started from the very beginning, i.e. with a certain
number of in the X-ray tube, I then calculated by means of existing
knowledge the number of Ka X-ray photons, next I put in all solid angles both
in the X-ray tube and the electron spectrometer and made some assumptions
about the effective photoelectron cross sections to expel electrons from the
outermost layers in a solid surface. Those electrons could not be expected to
suffer much energy loss and were the interesting ones upon which I should base
my spectroscopy. In retrospect, this last stage in my considerations was of
course of some interest, in view of the later development of electron spectrosco-
py into a surface spectroscopy. I guessed that what is now called the “escape
depth” of the electrons should be less than a light wavelength and more than a
few atomic layers and so I used 100 in my calculations. This was not too bad
a guess in consideration of later studies, indicating a lower figure for metals and
100 for organic multilayers. I finally arrived at an estimated counting rate on
a photoline in my apparatus of several thousands of electrons per minute as
recorded in the Geiger-Müller (G-M) counter placed at the focal plane in the
66 Physics 1981

double focusing spectrometer. Afterwards I was satisfied to find that this

calculation turned out to correspond fairly well to reality. This step, however,
in fact took several years to make.
The equipment which I had to build and test was at that time very compli-
cated. The resolution ultimately achieved turned out to be high enough to
enable recording even of the inherent widths of internal conversion lines [24].
This was done in 1954 and in 1956 I published [31] together with my collabo-
rator, Kay Edvarson, an account of this phase of the work under the title
ray Spectroscopy in the Precision Range of 1:10 5". In the next phase I had,
however, to overcome many difficulties in handling the low energy electrons
excited by X-rays and to record them by the G-M counter. This had an
extremely thin window through which gas diffused continuously and so was
compensated for by an automatic gas inlet arrangement. I did not realize, to
start with, the precautions I had to take when dealing with surfaces of solids in
order to record resolved line structures.
After some further testing of the equipment, concerning the influence of the
finite nuclear size on the conversion lines in some nuclei [32, 33], my two new
coworkers, Carl Nordling and Evelyn Sokolowski, and I finally made the
transition to atomic physics and were able to record our first photoelectron
spectrum [34, 35] with extremely sharp lines and with the expected intensities.
These electron lines definitely had all the qualities which I had set as my first
goal. They were symmetric, well defined and had linewidths which could be
deduced from the linewidth of the X-ray line used and the width of the atomic
level of the element under study, plus of course a small additional broadening
due to the resolution of the instrument. Fig. 1 shows an early recording of
MgO. The exact position of the peak of the electron lines could be measured
 K. M. Siegbahn 67

with considerable accuracy. Electron spectroscopy for atoms could be devel-

oped further with confidence.
Fig. 2 illustrates the steps which we took from the earlier recording of the
photoelectrons expelled from a gold foil by Robinson [36] in 1925 to the
introduction of the electron line spectroscopy in 1957. The dotted line inserted
in Robinson’s spectrum should correspond to the place where our spin doublet
N vIN vII to the right in the figure is situated. The distance between the two well
resolved lines in our spectrum would correspond to about 0.1 mm in the scale of
Robinson’s spectrum. Below this spectrum the black portion has been enlarged
(the gray scale) to show the corresponding part in our spectrum. This spectrum
was taken at a later stage of our development. Within this enlarged spectrum a
further enlargement of the N v I N vII doublet is inserted. The spin-orbit doublet
has now a distance between the lines which corresponds to a magnification of
600 times the scale in Robinson’s photographic recording.
A comparison between the middle and the lower spectrum in the figure
further demonstrates the extreme surface sensitivity of electron spectroscopy.
The difference between the two spectra is caused by a slight touch of a finger.
At the beginning this sensitivity caused us much trouble, but later on, when
electron spectroscopy was applied as a surface spectroscopy, it turned out to be
one of its most important assets.
In 1957 we published some papers [34, 35, 37] describing our first results,
which really did indicate great potential for the future. We also obtained our
first evidences of chemical shifts [37-42] for a metal and its oxides and for
Auger electron lines. I thought, however, that we should first improve our
techniques and explore purely atomic problems until we had achieved a greater
knowledge to enable us to progress to molecular problems. We therefore
systematically measured atomic binding energies for a great number of ele-
ments with much improved accuracy compared to previous methods, in par-
ticular X-ray absorption spectroscopy [40, 41, 43-61]. We were surprised to
find how inaccurate previously accepted electron binding energies for various
shells and elements could be. We made so-called “modified” Moseley dia-
grams. We were bothered by uncertainties due to the chemical state and
therefore tried to use only metals or at least similar compounds of the elements
in our systematic studies. We also devoted much effort to the investigation of
the Auger electron lines [62-69] which appeared in our spectra with the same
improved resolution as our photoelectron lines. As one of the results of such
studies we were able to observe for a group of elements around Z = 40 all the
nine lines expected in the intermediate coupling theory as compared to the
observed six lines in pure j-j coupling [63]. In general, in the spectroscopy we
developed photoelectron and Auger electron lines were found side by side.
Later on, therefore, we avoided any notation for this spectroscopy which could
give the false impression that only one of the two types of electron lines were
present. Auger electron lines can in addition to the X-ray mode of excitation also
be produced by electrons. Much of the above basic work on atomic energy
levels is described in theses by E. Sokolowski [70], C. Nordling [71], P.
Bergvall [72], 0. Hörnfeldt [73], S. Hagström [74] and A. Fahlman [75].
68 Physics 1981
 K. M. Siegbahn 69

After some years’ work in electron spectroscopy on problems in atomic

physics the next step came to the fore, namely to make systematic studies of the
chemical binding. This step was taken together with my coworkers Stig Hag-
Strom and Carl Nordling when Na2S2O 3 was found to give two well resolved K
photoelectron lines from the sulphur [76]. This showed that two differently
bonded sulphur atoms could be separated in the molecule, which according to
classical chemistry were in the -2 and the +6 valence states, respectively. This
was a more clear-cut case than the copper-copperoxide case we had studied
before, since the reference level for the two sulphur atoms could be traced to the
same molecule. The systematic investigation of chemical binding by means of
electron spectroscopy is described in theses by S.-E. Karlsson [77], R. Nord-
berg [78], K. Hamrin [79], J. H ed man [80], G. Johansson [81], U. Gelius [82]
and B. Lindberg [83].
Fig. 3 shows the chemically shifted Cls spectrum of ethyl trifluoroacetate [84,
85]. Fig. 4 [86] shows how the chemical shift effect can be used to identify
groups linked together in branched chains in polymers [87-90]. The intensi-
ties of the lines are correlated to the different branchings in the two viton
polymers.
In the interpretation of the electron spectra the first step is to consider the
electron structure as ‘frozen’ under the photoelectron emission process. In this
approximation the measured electron binding energies can be identified with
the Hartree-Fock energy eigenvalues of the orbitals. One then disregards the
fact that the remaining electronic structure, after electron emission, is relaxing
to a new hole state. This relaxation energy is by no means negligible and an
accurate calculation of the relevant binding energies has to include both the
ground state and the hole state energies as the difference between them. The
inclusion of relativistic effects in this treatment is essential for inner core
ionization and heavier elements (I. Lindgren [91]). More recently, methods
have been devised to describe the photoelectron emission by means of a
transition operator which properly accounts for the relaxation process [92-
94]. Various conceptual models complement the computational procedures on
an ab initio level.
For chemical shifts in free molecules, it is usually sufficiently accurate to
consider only the ground state properties [95-106]. This is due to the circum-

Fig.2. Electron spectra of gold.

Upper left: Spectrum recorded by Robinson in 1925 /36/. (Reproduced by due permission from
Taylor & Francis Ltd, London.)
Upper right: ESCA spectrum recorded in Uppsala before 1965 by non-monochromatized
excitation, The N VI, N VII levels are seen as two completely resolved lines in this spectrum whereas
the N v I N vII and O levels appear together as a hump in the photometric recording by Robinson
and are only barely visible on the photographic plate.
Middle: ESCA spectrum recorded in Uppsala 1972 by monochromatized excitation. The
magnification of this spectrum is 600 times that of Robinson.
Lower Part: ESCA spectrum of a gold foil with a fingerprint on the surface. The electron lines are
entirely due to the lingerprint whereas the gold lines are missing.
70 Physics 1981

Fig.3. The ESCA shifts of the Cls in ethyl trifluoroacetate. Upper spectrum without and lower with
X-ray monochromatization 184, 85).

Fig.4. ESCA spectra of Viton 65 and Viton 80 polymers.

 K. M. Siegbahn 71

stance that relaxation energies for a series of similar electronic systems vary
only marginally. This can be described by the division of the relaxation energy
into two contributions, one connected to the atomic contraction at ionization,
the other to the ‘flow’ of charge from the rest of the molecule [107, 108]. The
atomic part, which is very nearly constant for one specific element, is the
dominating contribution to the relaxation energy. The ‘flow’ part varies gener-
ally marginally for free molecules of similar structure, leading to constant
relaxation energies. There are cases, however, where the ‘flow’ part can signifi-
cantly change from one situation to another. One example is when a molecule
is adsorbed on a metal surface. In such a situation the flow of conduction
electrons from the metal substrate will contribute to the relaxation of the core
hole. This can increase the relaxation energy by several eV [109, 110]. Other
cases are pure metals and alloys where the conduction electrons are responsible
for the screening of the hole. [ 111 - 116]. These are treated in theses work by N.
[117] and R. Nyholm [118].
In view of the interesting applications which the chemical shift effect offered
for chemistry and the fact that at that time we had found that electron spectro-
scopy was applicable for the analysis of all elements in the Periodic System, we
coined the acronym ESCA, Electron Spectroscopy for Chemical Analysis. If
one is particularly interested in conduction bands for metals or alloys (Fig. 5

Fig. 5. Core and valence electron spectra (excited by monochromatized of some

C uxP d1-x, alloys, including the pure constituents. The binding energies undergo positive chemical
shifts with increasing Cu-content. The asymmetries of the lines are due to creation of soft electron-
hole pairs at the Fermi edge upon core ionization. The magnitude of the asymmetry is thus related
to the (local) density of states at the Fermi level. The Pd lines are seen to become more symmetric
as the Cu content increases (Pd local density of states decreases).
72 Physics 1981

Core

Fig.6. Regions of binding energies accessible with different photon sources

Solid circles: localized, atom-like orbitals.
Shaded area: more or less delocalized, molecular orbitals.

[119]) or valence electron structures of solid material in general, or free

molecules, more detailed notations can be preferred. One useful distinction is
between core and valence electron spectra (Fig. 6). Obviously, a further ground
of classification is due to the different origin of the photoelectron and Auger
electron lines, which both always occur in ESCA, as mentioned before. The
corresponding chemical shift effect for the Auger electron lines we established
soon afterwards [69] in the case of Na2S 2O 3. Further studies [ 111, 112, 120-
1331 have shown that the two shift effects are complementary. The combina-
tion of the two shifts provides insight into the mechanism of relaxation in the
photoionization process. Auger electron spectra are given in Fig. 7 for a clean
Mg metal, and when it is partly and finally fully oxidized to MgO [86].
Apart from the ordinary core electron lines and the Auger electron lines from
the various shells, all characteristic of each element, the electron spectra also
contain additional features. Satellites situated close to (~10 eV) the main core
lines at the low energy sides are often observed with intensities around 10% of
the latter. Fig. 8 [114] shows the electron spectrum of gaseous Hg. Inserted are
the satellites to the NvIN vII lines. Strong satellites were first observed [68] in
our spectra in the KLL Auger electron spectrum of potassium in some com-
pounds. Satellites have been found to occur frequently for core lines and
occasionally they can even have intensities comparable to the main lines, e.g.
paranitroaniline [134-136], t ransition metal compounds [137-146] and var-
 K. M. Siegbahn

3 1160

780

Fig. 7. MgKLL Auger electron spectra at different stages ofoxidation as obtained in ESCA. Upper
spectrum is from a clean metal surface, lower spectrum from the oxidized metal (with only a trace
of metal) and the middle spectrum is from an intermediate oxidation. Volume plasmon lines are
observed. For comparison, the positions of the NeKLL Auger electron lines are given below, as
recorded in the ESCA instrument by means of elcctron beam excitation.

ious adsorbed molecules on surfaces [148, 149]. Since these electrons can be
visualized as being emitted from excited states, the satellites were given the
name “shake-up” lines.
Molecules like O 2 or NO contain unpaired electrons and are therefore
paramagnetic. Large classes of solid materials have similar properties. In such
cases core electron spectra show typical features called spin-, multiplet-, or
exchange splitting. We first observed this phenomenon [150] in oxygen when
 Physics 1981

HOLE STATE
LEVELS

Fig. 8. Relation between the hole-state level system and observed photoelectron spectrum for the
mercury atom. The figure illustrates that the main lint-s are connected with states of the ion where
(in a one-electron picture) an atomic orbital has been removed from the neutral ground state. The
energy region close to the 4f-lines has been expanded (far right) to show that the additional satellite
lines observed (shake-up lines) are due to excitations above the 4f hole ground states.
(Note that the intensities of the 4f-lines have been truncated to fall into the scale of the figure.)
(From refs. 114 and 260.)

air was introduced into the gas cell in our ESCA instrument (Fig. 9). The 1s line
of O2 is split in the intensity ratio of 2:l. This spin splitting is due to the
exchange interaction between the remaining 1s electron and the two unpaired
electrons in the orbital, which are responsible for the paramagnetism of
this gas. The resulting spin can be either l/2 or 3/2. The corresponding
electrostatic exchange energies can be calculated and correspond well with the
measured splitting of 1.11 eV [ 151]. Apart from oxygen and nitrogen, argon
and CO2 can also be seen in air in spite of the low abundances of these gases. A
statistical treatment of the data even exhibits the presence of neon (0.001%).
Other particular features in the spectra occur in the valence electron region,
i.e. at binding energies extending from zero binding energy to say 50 eV. Our
first study of this entire region concerned ionic crystals like the alkali halides
[152].
In a later study [153] (1970) of a single crystal of NaCl we discovered the
phenomenon of ESCA diffraction. We investigated the angular distribution of
emitted Auger electrons from the NaKLL (1Dp) transition and the photoelec-
 K. M. Siegbahn 75

36

Fig. 9. Electron spectrum of air. The O1s is split into two components due to ‘spin’ or ‘multiplet’
splitting, Excitation was performed by means of monochromatized (Ahv = 0.2eV) radiation.

trons from the Nals, Na2s, C13p3/2 and the C13p levels, the latter being the
outermost valence orbital of the crystal. For excitation both and
were used. The crystal could from outside be set at different angular positions
relative to the emission direction of the electrons, which in turn was defined by
the slit system of the ESCA instrument. For comparison, the angular distribu-
tions from polycrystalline samples were also recorded. In all cases typical
diffraction patterns were found. In the control experiments on the polycrystal-
line samples there were no such patterns. Fig.10 shows two of the diffraction
patterns recorded. Subsequent measurements [154-158] on other single cry-
stals have shown agreement with the above investigation.
ESCA diffraction has more recently been applied to surface studies giving
interesting information on the geometry of adsorbed molecules [159-161] on
single crystals. This field is under development and should have a promising
future in surface science.
In X-ray diffraction there is an incoming photon wave and an outgoing
diffracted photon wave. In electron diffraction there is an incoming electron
wave and an outgoing diffracted electron wave. In ESCA diffraction there is an
76 Physics 1981

Fig. IO. Angular distributions of Cl2p3/2 photoelectrons and NaKLL (1D 2) Auger
electrons from a NaCl single crystal.

incoming photon wave and an outgoing diffracted electron wave with different
energies. These are three distinctly different physical phenomena which obvi-
ously require both different experimental equipment to observe and different
theoretical treatments to evaluate. With more suitably built instruments for
this purpose and with the addition of stronger X-ray sources and synchrotron
radiation [161-164] the development can proceed further.
In order to study gases and vapours from liquids, we first introduced a
freezing technique [165] to condense the gases onto the specimen plate. In this
way we obtained the valence or molecular orbital spectrum of solidified ben-
zene [166]. Soon afterwards we found that we could study the gaseous phase
just as well by introducing differential pumping in the instrument. Acetone was
our first study with this technique for gases, i.e. for free molecules, revealing
two well separated Cls core lines, one for the ketocarbon and one for the
methyl carbon in the intensity ratio of 1:2 [167].
 K. M. Siegbahn 77

Fig. 11. Schematic diagram of the liquid-sample arrangement

Since solids, surfaces, gases and vapours from liquids were all found to be
suitable samples in electron spectroscopy the question arose whether also
liquids could be studied. This turned out to be quite possible and several
satisfactory methods have been developed in our laboratory [168-173]. The
early methods and applications are described in theses by H. Siegbahn [174],
L. Asplund [175] and P. Kelfve [176]. Recently a new, more convenient
arrangement (H. Siegbahn) has been developed which is shown in Fig. 11
[173]. A small trundle is rotating in the sample cell in which the liquid is
introduced. A slit transmits the exciting radiation, e.g. X-radiation and the
expelled electrons from the continuously wetted trundle can leave the house
through a slit where differential pumping reduces the gas pressure. Cooling of
the sample has been introduced which has enabled a vast increase of the
number of liquids that can be studied. Fig. 12 shows part of a recent [173]
spectrum of ethanol as a solvent in which iodine and sodium iodide are
dissolved. One observes here a well resolved spin-orbit doublet of iodine 3d3,2
78 Physics 1981

Fig. 12. I3d spectrum from a solution of NaI (0.4M)+I 2 ( 0 . 4 M )in ethanol obtained at T = 200K.
The doublet for each spin-orbit component is due to ionization of the central atom (lower peak) and
outer atoms (higher peak) of the I 3, ion. The extra peaks at the high-binding-energy sides of each
spin-orbit component are interpreted as shake-up structures.

and 3d 5/2 . Each of these electron lines is chemically split in the ratio of
The interpretation is that has been formed in the solution. The centrally
located iodine has the highest binding energy. The correct intensity ratio of 1:2
is obtained when the shake-up satellites are ascribed to the two externally
situated iodine atoms, a conclusion which is in agreement with what we have
found for similar configurations in other electron spectra. Liquid ethanol itself
is shown in Fig. 13. Here one observes the oxygen 1s core line, the chemically
split carbon 1s line and the valence electron spectrum. The field of liquids is
presently in a state of rapid development.

Fig. 13. ESCA spectrum of liquid ethanol obtained at T = 200K.

 K. M. Siegbahn 79

In the valence region for free molecules it was possible to achieve much
improved resolution if UV light, especially the He resonance radiation at 21 eV
was used for excitation. Development work in this field was performed by D.
W. Turner [177-182] and W. C. Price [183, 184] and their coworkers in
England. The conduction bands of metals could be studied by a corresponding
technique using ultra-high vacuum (UHV) which was done by W. E. Spicer
and coworkers [185-188] in the USA.
In my laboratory a large electrostatic sector focusing instrument was de-
signed in the early part of the sixties for exciting electron spectra in the gaseous
phase by VUV radiation and also by electrons. High resolution valence elec-
tron spectra were thus obtained and furthermore Auger and autoionization
spectra of rare gases and organic molecules could be investigated at a resolu-
tion which enabled vibrational structures to appear also in the latter type of
spectra. Studies of angular distributions were initiated by using polarized
radiation. This was produced by VUV-polarizers which we developed in my
laboratory. Much of the above work is described in theses by T. Bergmark
[189], L. Karlsson [190], R. Jadrny [191] and L. Mattsson [192]. The Auger
electron spectroscopy was further explored in more recent publications [128,
132, 193-196].
The source of excitation was for a time confined to either the soft X-ray
region or the UV region with a gap between them from -50 eV (HeII) to 1250
eV Fig. 14 shows the valence spectrum of SF6 excited by HeI, He11
and [197, 198]. Some intermediate X-ray lines were later on added
[199-205], such as at 132 eV but the main step ofdevelopment was the
introduction during the seventies of the variable synchrotron radiation [e.g.
206-210] which partly bridged the gap. The previous strong distinction be-
tween X and UV excited electron spectra is therefore not so easy to maintain
any more unless one is emphasizing the particular technique at hand for
exciting the spectra. This is naturally not a trivial point for most researchers,
however, and excellent work can be done with one or the other technique alone
or in combination.
In 1967 we had gone through most of the basic features of the spectroscopy,
designed several new spectrometers (electrostatic double focusing ones includ-
ed), developed new radiation sources in the soft X-ray and UV region, made
theoretical investigations of the process of electronic relaxation at ionization
and applied the spectroscopy to a variety of different research fields. We then
decided to present the new spectroscopy in a more consistent and complete way
than we had done before. At the end of that year our book "ESCA-Atomic,
Molecular and Solid State Structure Studied by Means of Electron Spectro-
scopy” appeared [211]. Two years later we published a second book [212], this
time on "ESCA, Applied to Free Molecules”. At that time several instrumental
firms started to develop commercial instruments. I took part in one of these
developments at Hewlett-Packard in Palo Alto during a leave of abscence from
my laboratory in 1968. I spent that year at the Lawrence Berkeley Laboratory
with which we had had a long cooperation both in nuclear spectroscopy and
then in ESCA. The Hewlett-Packard instrument [213] was designed to include
80 Physics 1981

BINDING ENERGY

a monochromator for the AlKα radiation consisting of three spherically bent

quartz crystals and a retarding electrostatic lens system to match the dispersion
of these crystals to the electron spectrometer.
 The spherically bent quartz crystal monochromator, having the property of
being double focusing, was invented in my laboratory in 1958 [214] in quite
another connection, namely in low angle scattering of X-rays against latex and
other particles of biological interest [215]. The combination of double focusing
both in the X-ray monochromator and in the electron analyzer has turned out
to be essential for the further progress in ESCA. Other important technical
developments have been the introduction of swiftly rotating water cooled
anodes (U. Gelius), multidetector systems by means of electron channel plates
and computerization of the instruments (E. Basilier).
In 1972 my coworker Ulrik Gelius and I made a new instrument [85, 216]
with all these components included, in particular designed for the studies of
gases. With the improved resolution of this instrument new structures could be
resolved. One of principal interest was the discovery of the vibrational fine
structure of core lines [82, 217]. Fig. 15 shows the line profile of the Cls in
CH 4 It turns out that this line can be separated into three components caused
by the symmetric vibration when photoionization occurs in the 1s level of the
central carbon atom. When the photoelectron leaves the methane molecule the
latter shrinks about 0.05 A. The minimum of the new potential curve for the ion
will consequently be displaced by the corresponding amount and Franck-
Condon transitions which take place will then give rise to the observed vibra-

Fig. 15. Vibrational structure of the c o r e e l e c t r o n line (Cls in CH 4. The line structure can bc
quantitatively explained as a consequence of the shrinkage of the equilibrium distances upon core
electron mission /217/.
82 Physics 1981

tional fine structure of the electron line and with the intensities given by the
Franck-Condon factors. This finding can be correlated with the simultaneously
made discovery in our laboratory of vibrational fine structures in soft X-ray
emission lines [218-233]. This development is further described in theses work
by L. O. Werme [234], J. Nordgren [235] and H. [236]. Combined,
these results show that vibrations occur in these molecules during X-ray
emission both in the initial and the final states.
The above high resolution instrument designed together with U. Gelius was
planned to be a prototype instrument for a new generation of advanced
instruments which have now been constructed in a recently built laboratory for
electron spectroscopy in Uppsala [237]. These have just been finished and are
the sixth generation in the sequence from my laboratory since 1954. Two of the
new instruments are designed for molecular studies and the third for surface

Fig. 16. Side view of the new ESCA instrument for free molecules and condensed matter. The
instrument is UHV compatible and includes four diffcrent excitation modes (Monochromatized
Monochromatized and polarized UV; electron impact; monochromatized electron impact).
 K M. Siegbahn 83

studies. The spherical electrostatic analyzer (R=36 cm) is provided with an

electrostatic lens system due to B. Wannberg [238]. The modes of excitation
included in the instruments are: monochromatic radiation
eV) at 1486.6 eV; a UV light source with a grating providing selected UV lines
between 10 eV to ~50 eV; an electron monochromator of variable energy with
an energy homogeneity of 10 meV and an additional electron gun for Auger
electron excitation, also variable in energy (Fig. 16). A polarizer for the UV
light at different wavelengths can alternatively be used in angular distribution
studies.
The new instrument has been put into operation. As an illustration of its
improved qualities Fig. 17 shows a new investigation of the previously recorded
spectrum of methane (compare with Fig. 15) under increased resolution [261].
The vibrational structure is now well resolved. A convolution of the recorded
spectrum using the window curve of the spectrometer and a computer program
yields a remaining spectrum consisting of three narrow lines, the widths (~100
meV) of which can be measured with good accuracy. For calibration purposes
t h e A r 2 P 1 / 2 , 3 / 2 lines are simultaneously recorded. This investigation ap-
proaches an accuracy of a few meV in the determination of binding energies
around 300 eV, i.e. close to 1: 10 5.
The brief account I have given above concerns the work which was done in
my laboratory in the development of electron spectroscopy. During the seven-
ties several reviews and books on electron spectroscopy have been written and
for a complete account the reader has to go to such sources [239-258]. From
my own laboratory two new books have just been completed authored by Hans
Siegbahn and Leif Karlsson [259, 260], which cover developments mainly
after 1970 and present current experimental and theoretical aspects on electron
spectroscopy.
84 Physics 1981

292 0 291.5 291.0 290.5 290.0

Fig. 17. New study of the methane Cls core vibrational structure (compare Fig. 15) by means of the
instrument acc. to Fig. 16. The structure is resolved and deconvoluted into three narrow lines
which yield the binding energies and widths of the components to a high degree of accuracy. Argon
is used as a calibration gas. mixed with methane.
 K. M. Siegbahn 85

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2. Siegbahn K., and Svartholm N., Nature 157, 872 (1946).
3. Svartholm N., and Siegbahn K., Arkiv f. Mat. Astr., Fys. 33A, 21 (1946).
4. Hedgran A., Siegbahn K., and Svartholm N., Proc. Phys. Soc. A63, 960 (1950).
5. Siegbahn K., in Alpha-. Beta- and Gamma-Ray Spectroscopy, ref. 25, p. 79.
6. Hofstadter R., Les Prix Nobel, 1961.
7. Lindström G., Nuclear Resonance Absorption Applied to Precise Measurements of Nuclear
Magnetic Moments and the Establishment of an Absolute Energy Scale in P-Spectroscopy
(Thesis). Ark. Fysik 4, 1 (1951).
8. Hedgran A., Precision Measurements of Nuclear Gamma-Radiation by Techniques of Beta-
Spectroscopy (Thesis), Almqvist & Wiksell. Uppsala 1952.
9. Bergström I., The Isomers of Krypton and Xenon: An Investigation with Eletromagnetically
Separated Radioactive Isotopes (Thesis). Ark. Fysik 5. 191 (1952).
10. Thulin S., Studies in Nuclear Spectroscopy) with Electromagnetically Separated Gaseous
Isotopes (Thesis), Almqvist & Wiksell, Uppsala 1954.
11. Gerholm T.R., Coincidence Spectroscopy; Studies of Nuclear Magnetic Dipole Transition
Probabilities and of Positron Annihilation Lifetimes. Design and Construction of an Electron-
Electron Coincidence Spectrometer and Its Application to the Investigation of Some Complex
Nuclear Disintegrations (Thesis). Almqvist & Wiksell. Uppsala 1956.
12. Lindqvist I‘., Angular Correlation Measurements: Studies of Relative Transition Probabil-
itirs of Gamma Radiation and of Internal Compton Effect. Experiments on Nuclear g-Factors
(Thesis), Almqvist & Wiksell, Uppsala 1957.
13. Bäckström G.. Levels and Transitions of Atomic Nuclei: Experiments and Experimental
Methods (Thesis), Almqvist & Wiksell, Uppsala 1960.
14. Pettersson B.-G., Experimental Studies of Electron-Gamma Directional Correlations (The-
sis), Almqvist & Wiksell, Uppsala 196 1.
15. Karlsson E., Studies of Excitation Modes of Atomic Nuclei by Means of Magnetic Moment
Determinations and General Decay Investigations (Thesis). Acta Universitatis Upsaliensis
11 , 1962.
16. Thun J.E., Studies of Nuclear Properties of Decay Modes of Radioactive Nuclei; Directional
Correlation and Coincidence Investigations (Thesis). Acta Universitatis Upsaliensis 15,
1962.
17. Lindskog J., Studies of Nuclear Properties by Coincidence Spectrometer Methods; Decay
Schemes and Transition Probabilities (Thesis), Acta Universitatis Upsaliensis 22. 1963.
18. Matthias E., Experimental and Theoretical Investigations of Perturbed Angular Correlations
(Thesis), Almqvist & Wiksell, Uppsala 1963.
19. Schneider W., Applications of Digital Computer Techniques to Theoretical Investigations
and the Analysis of Experimental Data in Nuclear Spectroscopy (Thesis), Almqvist &
Wiksell, Uppsala 1963.
20. Bergman O., Experimental Studies of Nuclear States and Transitions (Thesis), Acta Univer-
sitatis Upsaliensis 41, 1964.
21. Sundström T, Electromagnetic Transitions in Atomic Nuclei: Experimental Studies of Tran-
sition Probabilities and Decay Schemes (Thesis). Acta Universitatis Upsaliensis 47, 1964.
22 Klcinheinz P., Studies of Internal Conversion Transitions in the Decay of Excited Nuclear
States (Thesis), Almqvist & Wiksell, Uppsala 1965.
23. Bäcklin A., Nuclear Levels Excited in Ncutron Capture Reactions and Radioactive Decays
(Thesis), Acta Universitatis Upsaliensis 96, 1967.
24. Siegbahn K. (Editor), Beta- and Gamma Ray Spectroscopy, North-Holland Publ. Co.,
Amsterdam, 1955.
25. Siegbahn K. (Editor), Alpha-. Beta and Gamma Ray Spectroscopy, North-Holland Publ.
Co., Amsterdam, 1965.
26. Jenkin J.G., Leckey R.C.G. and Liesegang J., J. Electron Spectrosc. 12, I (1977).
86 Physics 1981

27. Carlson T.A. (Editor), X-ray Photoelectron Spectroscopy, Benchmark Papers in Phys. Chem.
and Chem. Phys. Vol. 2, Dowden, Hutchinson and Ross (1978).
28. Siegbahn K., Conf. of the Swedish Nat. Committee for Physics, Stockholm, 1952, Ark. Fys. 7,
86 (1954).
29. Siegbahn K., Conf. of the Swedish Nat. Committee for Physics, Stockholm, 1953, Ark. Fys. 8,
19 (1954).
30. Siegbahn K., Introductory Talk at the Int. Conf. on Beta and Gamma Radioactivity,
Amsterdam, 1952; Physica 18, 1043 (1952).
31. Siegbahn K. and Edvarson K., Nucl. Phys. 1, 137 (1956).
32. Sokolowski E., Edvarson K. and Siegbahn K., Nucl. Phys. 1, 160 (1956).
33. Nordling C., Siegbahn K., Sokolowski E. and Wapstra A.H., Nucl. Phys. I, 326 (1956).
34. Nordling C., Sokolowski E. and Siegbahn K., Phys. Rev. 105, 1676 (1957).
35. Sokolowski E., Nordling C. and Siegbahn K., Ark. Fysik. 12, 301 (1957).
36. Robinson H., Phil. Mag. 50, 241 (1925).
37. Siegbahn K., Nordling C. and Sokolowski E., Proc. Rehovoth Conf. Nucl. Structure, North-
Holland Publ. Co., Amsterdam, 1957, p. 291.
38. Sokolowski E., Nordling C. and Siegbahn K., Phys. Rev. 110, 776 (1958).
39. Nordling C., Sokolowski E. and Siegbahn K., Arkiv Fysik 13, 282 (1958).
40. Sokolowski E., Nordling C. and Siegbahn K., Arkiv Fysik 13, 288 (1958).
41. Nordling C., Sokolowski E. and Siegbahn K., Arkiv Fysik 13, 483 (1958).
42. Sokolowski E. and Nordling C., Arkiv Fysik 14, 557 (1959).
43. Sokolowski E., Arkiv Fysik 15, 1 (1959).
44. Nordling C., Arkiv Fysik 15, 241 (1959).
45. Nordling C., Arkiv Fysik 1.5, 397 (1959).
46. Nordling C. and Hagström S., Arkiv Fysik 15, 431 (1959).
47. BergvaIl P. and Hagström S., Arkiv Fysik 16, 485 (1960).
48. Nordling C. and Hagström S., Arkiv Fysik 16, 515 (1960).
49. Bergvall P. and Hagström S., Arkiv Fysik 17, 61 (1960).
50. Bergvall P., Hörnfeldt 0. and Nordling C., Arkiv Fysik 17, 113 (1960).
51. Nordling C., Hagström S. and Siegbahn K., Arkiv Fysik 22, 428 (1962).
52. Fahlman A., Hörnfeldt 0. and Nordling C., Arkiv Fysik 23, 75 (1962).
53. Hagström S., Hörnfeldt O., Nordling C. and Siegbahn K. Arkiv Fysik 23, 145 (1962).
54. Hagström S., Nordling C. and Siegbahn K., “Alpha-, Beta- and Gamma-Ray Spectroscopy”,
Appendix 2. Ed.Siegbahn K., North-Holland Publ. Co., Amsterdam 1965.
55. Hagström S. and Karlsson S.-E., Arkiv Fysik 26, 252 (1964).
56. Hagström S. and Karlsson S.-E., Arkiv Fysik 26, 451 (1964).
57. Fahlman A. and Hagström S., Arkiv Fysik 27, 69 (1964).
58. Andersson I. and Hagström S., Arkiv Fysik 27, 161 (1964).
59. Nordling C. and Hagström S., Z. Phys. 178, 418 (1964).
60. Fahlman A., Hamrin K., Nordberg R., Nordling C. and Siegbahn K., Phys. Rev. Lett. 14, 127
(1965).
61. Fahlman A., Hamrin K., Nordberg R., Nordling C., Siegbahn K. and Holm L.W., Phys.
Lett. 19,643 (1966).
62. Hörnfeldt 0. and Fahlman A., Arkiv Fysik 22, 412 (1962).
63. Hörnfeldt O., Fahlman A. and Nordling C., Arkiv Fysik 23, 155 (1962).
64. Hörnfeldt O., Arkiv Fysik 23, 235 (1962).
65. Hagström S., Z. Phys. 178, 82 (1964).
66. Fahlman A. and Nordling C. Arkiv Fysik 26, 248 (1964).
67. Fahlman A., Nordberg R., Nordling C. and Siegbahn K., Z. Phys. 192, 476 (1966).
68. Fahlman A., Hamrin K., Axelson G., Nordling C. and Siegbahn K., Z. Phys. 192,484 (1966).
69. Fahlman A., Hamrin K., Nordberg R., Nordling C. and Siegbahn K., Phys. Lett. 20, 159
(1966).
70. Sokolowski E., Investigations of Inner Electron Shells by Spectroscopic Studies of Photo- and
Auger Electrons (Thesis), Almqvist & Wiksell, Uppsala 1959.
 K M. Siegbahn 87

71. Nordling C., Experimental Studies of Electron Binding Energies and Auger Spectra (Thesis),
Almqvist & Wiksell, Uppsala 1959.
72. Bergvall P., Investigations of Atomic and N u c l e a r Energy Levels by Crystal Diffraction and
Photo Electron Spectroscopy (Thesis), Almqvist & Wiksell, Uppsala 1960.
73. Hörnfeldt O., Studies of Atomic Level Energies and Auger Spectra (Thesis), Almqvist &
Wiksell, Uppsala 1962.
74. Hagström S., Studies of Some Atomic Properties by Electron Spectroscopy (Thesis), Alm-
qvist & Wiksell, Uppsala 1964.
75. Fahlman A., Electron Spectroscopy of Atoms and Molecules (Thesis), Acta Universitatis
Upsaliensis 73, 1966.
76. Hagström S., Nordling C. and Siegbahn K., Phys. Lett. 9, 235 (1964).
77. Karlsson S.-E., Precision Electron Spectroscopy for Studies of Nuclear and Atomic Energy
Levels (Thesis), Acta Universitatis Upsaliensis 99, 1967.
78. Nordberg R., ESCA Studies of Atoms and Molecules (Thesis), Acta Universitatis Upsaliensis
118, 1968.
79. Hamrin K., ESCA Applied to Solids and Gases (Thesis), Acta Universitatis Upsaliensis 151,
1970.
80. Hedman J,, ESCA Studies of Electron Levels and Bands in Atoms, Molecules and Solids
(Thesis), Acta Universitatis Upsaliensis 196, 1972.
81. Johansson G., Chemical Bonding and Electronic Structure of Molecules and Solids Studied
by ESCA (Thesis), Acta Universitatis Upsaliensis 205, 1972.
82. Gelius U., Molecular Spectroscopy by Means of ESCA; Experimental and Theoretical
Studies (Thesis), Acta Universitatis Upsaliensis 242, 1973.
83. Lindberg B., Some Aspects of the Sulphur-Oxygen Bond in Organic Sulphur Groups (The-
sis), Acta Universitatis Upsaliensis 173, 1970.
84. ESCA I, ref. 211, p. 21.
85. Gelius U., Basilier E., Svensson S., Bergmark T. and Siegbahn K., J. Electron Spectrosc. 2,
405 (1974).
86. Siegbahn K., ibid. 5, 3 (1974).
87. Clark D.T., Dilks A., Shuttleworth S. and Thomas H.R., ibid., 14, 247 (1978).
88. Clark D.T. and Dilks A., J. Polymer Sci. 16, 911 (1978).
89. Clark D.T., Phys. Scr. 16. 307 (1977).
90. Clark D.T., in Handbook of X-ray and UV Photoelectron Spectroscopy (Ed. D. Briggs)
Heyden 1977, p. 211.
91. ESCA I, ref. 211 , sect 111-9, p. 63.
92. Goscinski O., Howat G. and T., J. Phys. B8, 11 (1975).
93. Pickup B. and Goscinski O., Mol. Phys. 26: 1013 (1973).
94. Goscinski O., Hehenberger M., Roos B. and Siegbahn P., Chem. Phys. Lett. 33, 427, (1975).
95. ESCA II, ref. 212. Sect. 5.4.
96. Gelius U., Hedén P.-F., Hedman J., Lindberg B.J., Manne R.. Nordberg R., Nordling C. and
Siegbahn K., Phys. Scr. 2, 70 (I 970).
97. Lindberg B..J., Hamrin K., Johansson G., Gelius U., Fahlman A., Nordling C. and Siegbahn
K., Phys. Scr. I, 286 (1970).
98. Allison D.A., Johansson G., Allan CJ., Gelius U., Siegbahn H., Allison J. and Siegbahn K.,
J. Electron Spectrosc. 1, 269 (1972/73).
99. Shirley D.A., Adv. Chem. Phys. 23, 85 (1973).
100. Clark D.T., in Electron Emission Spectroscopy. (Eds. Dekeyser et al.) D. Reidel Publ. Co.
(1973).
101. Davis D.W., Banna MS. and Shirley D.A., J. Chem. Phys. 60, 237 (1974).
102. Wyatt J.F., Hillier I.H., Saunders V.R., Connor J.A. and Barber M., J. Chem. Phys. 54, 531l
(1971).
103. Jolly W.L. and Perry W.B., Inorg. Chem. 13, 2686 (1974).
104. Jolly W.L. and Perry W.B., J. Amer. Chem. Soc. 95, 5442 (1974).
105. Carver, J. C., Gray R. C. and Hercules, D. M., J. Amer. Chem. Soc. 96, 6851 (1974).
106. Perry, W. B. and Jolly, W. L., Inorg. Chem. 13, 1211 (1974).
88 Physics 1981

107. Gelius, U., Johansson, G. Siegbahn, H. Allan, C. J., Allison, D. A., Allison J. and Sicgbahn,
K., J, Electron Spectrosc. 1, 285 (1972173).
108. Siegbahn. H., Mcdeiros R. and Goscinski, O. ibid. 8, 149 (1976).
109. Bagus P. S. and Hermann, K., Solid State Comm. 20, 5 (1976).
110. Ellis, D. E., Baerends, E. J., Adachi H. and Averill, F. W., Surf. Sci. 64, 649 (1977).
111. Ley, L. Kowalczyk, S. P.. McFeely, F. R., Pollak R. A., and Shirley, D. A. Phys. Rev. B8,
2392 (1973).
112. Kowalrzyk. S. P., Pollak. R. A.. McFeely, F. R., Lcy L. and Shirley, D. A., ibid. B 8 , 2 3 8 7
(1973).
113. Shirley, D. A., Martin. R. L., Kowalczyk. S. P.. McFeely F. R. and Ley, I,.. Phys. Rev. B 1 5 ,
544 (1977).
114. Svensson, S.. N . , Basilicr, E., Malmquist, P. Gelius U. and Siegbahn, K., J.
Electron Spcctrosc. 9, 51 (1976).
115. Jen, J. S. and Thomas, T. D.. Phys. Rev. B13, 5284 (1976).
116. Johansson B. and N.. ibid. B21. 4427 (1980).
117. N., Atomic, Molecular and Solid State Effects in Photoelectron Spectroscopy
(Thesis), Acta Universitatis Upsalicnsis 579. Uppsala 1980.
118. Nyholm. R., Electronic Structure and Photoionization Studied by Electron Spectroscopy
(Thesis). Acta Universitatis Upsaliensis 581, Uppsala 1980.
119. N., Nyholm, R., Calén. H.. Hedman, J. and Johansson. B. Uppsala University,
Institute of Physics Report, UUIP-1008 (July 1980).
120. Kowalczyk, S. P., Pollak. R. A., McFerly. F. R. and Shirley, D. A., Phys. Rev. B 8 , 3 5 8 3
(1973).
121. Kowalczyk. S. P.. Ley. L., McFeely. F. R., Pollak, R. A. and Shirley, D. A.. Phys Rev. B 9 ,
381 (1974).
122. Wagner. C. D. and Biloen, P. Surf. Sci. 35. 82 (1973).
123. Matthew, J. A. D.. Surf. Sci. 40, 451 (1973).
124. Utriainen, J., Linkoaho. M. and T.. in Proc. Int. Symp. X-ray Sp. and El. Str. of Mat.
1, 382 (1973).
125. Asplund, L., Kelfve, P., Siegbahn. H.. Goscinski. 0.. Fellncr-Feldegg, H., Hamrin, K.,
Blomster. B. and Siegbahn. K., Chem. Phys. Lett. 40, 353 (1976).
126. Keski-Rahkoncn. O. and Krause. M. O., J. Electron Spectrosc. 9, 371 (1976).
127. Sieghahn. H. and Goscinski. 0.. Phys. Scr. 13. 225 (1976).
128. Asplund, L, , Kelfve, P., Blomstcr, B., Siegbahn. H.. Siegbahn, K., Lozes, R. L. and Wahlgren
U. I., Phys. Scr. 16. 273 (1977).
129. Kim, K. S., Gaarcnstroom. S. W. and Winograd, N.. Chem. Phys. Lett. 41, 503 (1976).
130. Wagner, C. D., Far. Disc. Chem. Soc. 60, 291 (1975).
131. Wagner. C. D., in Handbook of X-ray and Ultraviolet Photoelectron Spectroscopy (Ed. D.
Briggs) Chapt. 7 (Heyden. 1977).
132. Kelfvc, P.. Blomster, B., Siegbahn, H., Siegbahn. K., Sanhueza, E. and Goscinski O., Phys.
Scr. 21, 75 (1980).
133. Thomas. T. D., J. Electron Spectrosc. 20. 117 (1980).
134. ESCA I, ref. 21 1. p. 118.
135. Pignataro, S. and Distefano. G., J, Electron Spectrosc, 2, 171 (1973). Z. Naturforsch. 30a, 815
(1975).
136. H., Roos, B., Bagus, P. S., Gelius. U., Malmquist, P. Svensson, S., Maripuu, R.
and Siegbahn, K., Uppsala University, Institute of Physics Report, UUIP-1057 (1982).
137. Yin, L., Adler, I., Tsang, T., Mantienzo, L. J. and Grim, S. O., Chem. Phys. Lett. 24, 81
(1974).
138. Pignataro, S., Foffani, A. and Distefano, G., Chem. Phys. Lett. 20, 350 (1973).
139. Johansson, L. Y., Larsson, R.. Blomquist, J.. Cederström, C., Grapengiesser, S., Hclgeson,
U., Moberg, L. C. and Sundhom, M., Chem. Phys. Lett. 24, 508 (1974).
140. Barber, M., Connor, J, A. and Hillier, I. H., Chem. Phys. Lett. 9, 570 (1971).
141. Hüfner, S. and Wertheim, G. K., Phys. Rev. B7. 5086 (1973).
142. Rosencwaig, A., Wertheim, G. K. and Guggenheim, H. J.. Phys. Rev. Lett. 27, 479 (1971).
 K. M. Siegbahn 89

143. Rosencwaig, A. and Wertheim, G. K., J. Electron Spectrosc. 1, 493 (1973).

144. Frost, D. C., McDowell, C. A. and Woolsey, I. S., Chem. Phys Lett. 17, 320 (1972).
145. Kim, K. S., Chem. Phys. Lett. 26, 234 (1974).
146. Carlson, T. A., Carver, J. C., Saethre, L. J., Santibanez, F. G. and Vernon, G. A., J. Electron
Spectrosc, 5, 247 (1974).
147. Fuggle, J. C., Umbach, E., Menzel, D., Wandelt, K. and Brundle, C. R., Solid State Comm.
27,65 (1978).
148. Lang, N. D. and Williams, A. R., Phys. Rev. B16, 2408 (1977).
149. Schönhammer, K. and Gunnarsson. 0.. Solid State Comm. 23. 691 (1978) and 26. 399 (1978)
and Z., Phys. B30, 297 (1978).
150. Hedman, J., Hedén. P. F.. Nordling, C. and Siegbahn. K., Phys. Lett. A29. 178 (1969).
1.51. ESCA II. ref 212, section 5.1, p 56.
152. ESCA 1, ref. 21 I, section IV, p. 72.
153. Siegbahn, K.. Gelius, U.. Siegbahn. H and Olsson. E., Phys. Lett. 32A. 221 (1970) and Phys.
Scr. I. 272 (1970).
1.54. Fadley, C. S. and Bergström S. I,.. Phys Lett. 35A, 373 (1971).
155. Baird. R.J., Fadley. C. S. and Wagner. I,. F.. Phy. Rev. B15. 666 (1977).
136. Zehner, D.M., Noonan, J. R. and Jenkins. L. H.. Phys. Lett. 62A. 267 (1977).
157. Briggs. D.. Marbrow. R. A. and Lambert. R. M . Solid State Comm. 25. 40 (1978).
158. Erickson. N. E.. Phys. Scr. 16, 462 (1977).
159. Kono, S.. Goldberg, S. M.. Hall, N. F. T. and Fadley. C S.. Phys. Rev. Lett. 41, 1831 (1978).
160. Petersson, L.. G.. Kono. S.. Hall. N. F T.- . Fadley C S. and Pendry, J B.. Phys. Rev. Lett 42,
1545 (1979).
161. Woodruff, D. P., Norman. D.. Holland. B. W., Smith. N. W., Farrell. H. H. and Traum. M..
M.. Phys. Rev. Lett. 41, 1 130 (1978).
t 62. Kevan. S. D., Rosenblatt. D.. H . Denley. D. R.. Lee. B.-C:. and Shirley. D. A., Phys. Rev. B20.
4133 (1979); Phys. Rev. Lett. 41. 156.5 (1978).
163. McGovern, I. T.. Eberhardt. W. and Plummer. E. W.. Sol. St. Comm. 32, 963 (1979).
164. Guillot. C., Jugnet. Y., l,asailly, Y., Lecante, J., Spanjaard. D. and Duc. T. M. (private
communication. 1980).
165. Bergmark. T . Magnusson. N. and Siegbahn. K.. Ark. Fys. 37. 3.53 (1968).
166. ESCA I. ref. 211 , p 20.
167. ESCA I. ref. 211, p. 21.
168. Siegbahn. H. and Siegbahn. K., J. Electron Spretrosc. 2. 319 (1973).
169. Sieghahn. H.. Asplund, L., Kelfve. P.. Hamrin. K.. Karlsson. I,. and Siegbahn. K. ,J
Electron Spectrosc. 5, 1059 (1974).
170. Siegbahn. H.. Asplund. L.. Kelfve. P. and Siegbahn. K., J. Electron Spectrosc. 7. 411 (1975).
171. Fellner-Feldegg. H.. Siegbahn. H.. Asplund. I... Kellfve. P. and Siegbahn. K., ,J. Electron
Spectrosc. 7. 421 (197.5).
172. Lindberg. B Asplund. L., Fellner-Feldegg. H.. Kelfve. I’.. Siegbahn. H. and Siegbahn K..
Chem. Phys. Lett. .79, 8 (1976).
173. Siegbahn. H.. Svensson, S. and Lundholm. M., ,J. Electron Spectrosc. 24, 205 (1981). The first
considerations of continuously renewable liquid samples in vacuum for ESCA and experi-
ments on liquid beams were reported at the Asilomar conference 1971: K. Siegbahn: Perspec-
tives and Problems in Electron Spectroscopy. (Editor: D. Shirley), North Holland, 1972.
Further accounts for these developments arc found in ref. /168/-/172/. Different suggested
alternatives for handling the renewable samples (liquid beams, wetted rotating wires and
rotating disks) were presented at the Namur Conference 1974, K. Siegbahn: Electron Spec-
troscopy-An Outlook (secs 3 and 4, figs 5-10). Editors: R. Caudano and J. Verbist, Elsevier,
1974. References to recent other works on liquids are found in H. Siegbahn ct. al. ref. /173/
(R. Ballard et. al. see ref. ibid. 6 and 7: P. Delahay et. al. ref. ibid. 8-10; K. Burger et. al. ref.
ibid. 11 and 12; S. Avanzino and W. ,Jolly ref ibid. 13).
174. Siegbahn, H., ESCA Studies of Electronic Structure and Photoionization in Gases, Liquids
and Solids (Thesis), Acta Universitatis Upsaliensis 277, Uppsala 1974.
90 Physics 1981

175. Asplund, L., Electron Spectroscopy of Liquids and Gases (Thesis), Acta Universitatis Upsa-
liensis 409, Uppsala 1977.
176. Kelfve, P., Electronic Structure of Free Atoms, Molecules and Liquids Studied by Electron
Spectroscopy (Thesis), Acta Universitatis Upsaliensis 483, Uppsala 1978.
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