Intermetallic Compounds – Principles and Practice – Volume 3: Progress.
Edited by J. H. Westbrook, R. L. Fleischer
Chapter 7
Spectroscopic Approaches
Esther Belin-Ferré
Universite´ Pierre et Marie Curie – Centre National de la Recherche Scientifique, Paris, France
1. Introduction
The properties of intermetallics may be better under-
stood through insight into their electronic as well as
their atomic structures. Knowledge of the electronic
structure and the nature of bonding may also give
general trends, helpful when looking either for new
intermetallics or for improving physical characteristics
along definite lines such as enhancing resistance to
corrosion, modifying mechanical properties, etc. There-
fore, numerous theoretical as well as experimental means
have been developed to analyse the band structure and
densities of electronic states (DOS) of these solids. For
further background the reader may wish to consult the
following chapters from Vol. 1 of this treatise: Turchi,
Ch. 2, on electronic theories of phase stability; Singh,
Ch. 6, on band structures and their interpretation; and
Pintschovius, Ch. 7, on phonon dispersion curves and
their interpretation.
In this chapter a few experimental spectroscopic
techniques will be presented. These are interesting as
far as electronic structure is concerned because they
investigate transitions between two different quantum
states of the solid, each one characterized by its energy
and lifetime. Accordingly they provide direct relevant
information on the nature and energy distribution of
the electronic states and their interactions, therefore on
the chemical bonds in the material. Total overlap of
partial electronic bands in the valence band of a
specimen implies a complete mixing of the correspond-
ing states and suggests metallic or covalent bonding
which is generally found for hard materials. Changes
of the electronic and physical properties from one
sample to another involve modifications in the electro-
nic structure, for example, deviation of the electronic
Intermetallic Compounds: Vol. 3, Principles and Practice. Edited by J. H. Westbrook and R. L. Fleischer.
B 2002 John Wiley & Sons, Ltd.
Copyright & 2002 John Wiley & Sons Ltd
ISBNs 0-471-49315-5 (Hardback); 0-470-84585-6 (Electronic)
energy distributions for a given intermetallic with
respect to free-electron or d-like metals will underline
that the specimen departs from a metallic-like beha-
viour. Also, shift of the valence and conduction band
edges from the Fermi level will end up in the formation
of a pseudo-gap or a real gap which clearly will imply
deviation from metallic behaviour.
We are not going to consider here all of the
numerous spectroscopic techniques useful for inves-
tigating the electronic structure of solids (visible, UV
and infra-red optical spectroscopies, Raman, NMR,
ellipsometry . . .) but will restrict ourselves to only a
few which we have chosen because they give direct
information on the electronic distributions and can
be compared directly with DOS calculations with no
further assumptions and do not require sophisticated
specimen preparation. These are photoemission, soft
X-ray emission, X-ray photoabsorption, electron
energy loss, and isochromat Bremsstrahlung spectro-
scopies. The first two techniques allow one to analyse
electronic occupied states whereas the last three are
well adapted to a description of the electronic distri-
butions of normally unoccupied states. For each of
these techniques, the underlying general principles
will be presented. Their usefulness and main
characteristics will be illustrated with only a few
selected recent examples of their application to
intermetallics presented from the large volume of the
experimental information published so far.
2. Investigation of Occupied States
As mentioned, the occupied electronic states of a solid can
be probed by means of photoemission and soft X-ray
136 Bonding and Stability
Figure 1 Scheme of the energy levels involved in binding
energy measurements. EF is the Fermi level. EK(V) is the kinetic
energy with respect to the vacuum energy level of the sample,
and EB is the binding energy of the photoelectron created by
the incoming photons. It is measured with a spectrometer
having the work function spectrom
emission spectroscopies. For a few decades now, since
the original work of K. Siegbahn and his group in
Uppsala (Siegbahn et al., 1967, 1969), so-called ESCA
(electron spectroscopy for chemical analysis) or
photoemission spectroscopy (PES) has become quite
a popular technique, so much so that very efficient and
powerful spectrometers are produced and marketed by
various companies. On the contrary, for soft X-ray
emission spectroscopy, appropriate spectrometers are
not commercially available; they mostly have to be
designed and constructed in the laboratories that
intend to use this technique. However, this situation
will not long prevail for nowadays several groups, all
around the world, operate such home-made equip-
ments using the very intense light beams of new
generation synchrotron facilities.
2.1 Photoemission Spectroscopies
Photoemission spectroscopies (PES) probe the kinetic
energies EK of photoelectrons emitted from inner levels
of a solid as well as from the outermost occupied band
(OB) as a consequence of the interaction of the solid
with an incoming X-ray (XPS) or ultra-violet (UPS)
radiation of energy hn. Therefore, the initial state is the
ground state of the system whereas in the final state
there is a hole created by the incoming energetic beam.
Within the framework of the frozen orbitals (assuming
that the presence of a hole in the final state does not
affect significantly the remaining orbitals), the
photoemission process involves three successive steps:
first, the excitation of the photoelectron, second, its
travel through the solid and third, its ejection into the
vacuum from the very surface. This last step is
governed by the photoelectron transmission probabil-
ity. Accordingly, the binding energy EB of the
photoelectron is related to its kinetic energy by:
EK ¼ hn
EB
 ð1Þ
where  denotes the difference between the work
functions of the spectrometer and of the sample
(Figure 1). Usually, it is not necessary to know 
exactly provided the EB scale is properly calibrated,
e.g. by referring to a well-known level such as the 1s
level of contaminating carbon, always present at the
surface of a sample not prepared in a clean, high
vacuum, or the Au 4f7=2 levels if Au can be evaporated
onto the sample itself. It is to be noted that the Fermi
levels of the spectrometer and metallic specimens
adjust to each other, whereas this does not hold true
for non-conducting substances for which charging
effects induce shifts that can be as large as several eV.
As to the final energy resolution of PES measurements,
it depends upon the natural energy width of the incident
photon beam and the spectrometer experimental func-
tion. For XPS it is generally about 0.4–0.8 eV and for
UPS it may be as good as a few tenths of an eV.
The binding energies of the inner levels of a specimen
are obtained separately. On the contrary, for the OB, the
contributions of all the electrons are summed, modu-
lated by the photoelectron cross-sections s:
s / hn jh f jrj i ij ð2Þ
where f and i denote the wave functions of the final
and initial states, respectively.
During its travel through the solid, the photo-
electron is subjected to inelastic interactions with the
electrons of the medium; therefore, the sampled depth
is governed by the mean free path of the photoelec-
trons, denoted . Thickness up to 3 are generally
probed, which makes PES basically a surface-sensitive
technique. Consequently, it is necessary to use very
careful preparation and characterization of the surface
under study. In addition, because of the inelastic
interactions, the shape of the background on which the
photoelectron peaks are superposed is not a simple
function, and it is necessary to model it. In narrow
energy ranges, say for instance for inner level peaks, a
linear background can be subtracted, but this cannot
be done for OB states that usually extend over more
than 10–12 eV.
 Spectroscopic Approaches 137
The number nðEÞ of the emitted photoelectrons is a
function of several parameters and can be written as

nðEÞ / nðhnÞ.NðEÞi .NðEÞf . fFD .sðEÞ.AðEÞ ð3Þ

where nðhnÞ is the number of incident photons, NðEÞi

and NðEÞf stand for the DOS at initial and final states,
respectively, fFD is the Fermi–Dirac temperature
function, sðEÞ is the photoemission cross-section and
AðEÞ is the detector transmission factor. The contribu-
tion to the total intensity due to an element E at a
depth x in a direction referred to by its angle y with the
surface of the sample is connected to its concentration
and to the electron’s mean free path. Therefore,
accurate measurements of the intensity of a chosen
core level of a given element in a sample make it
possible to determine its concentration by comparing
the same photoelectron peak in the specimen and the
pure element. Also, profile variations in concentration
can be achieved by tuning the angle y.
There are two kinds of PES techniques by which
final states may be explored. In integrated photoemis-
sion all possible final states contribute to the spectra.
As photoemission cross-sections depend on hn, tuning
the energy of the incident photons allows one to
achieve some site selectivity and to distinguish between
the features due to individual contributions to the OB
of an alloy, provided their respective EB values are
different enough to be resolved experimentally. Yet,
the photoemission cross-sections significantly favour d
and f states relative to p or s states (Yeh and Lindau
1985; Yeh, 1993). Accordingly, no features arising
from sp constituents are observed in the OB spectra of
alloys which contain sp as well as d and f elements.
This integrated photoemission technique is mainly
applied to polycrystalline specimens. The experimental
data are usually compared to total DOS calculations
when available. Such comparison is made more mean-
ingful by convoluting the theoretical DOS with
Figure 2 Panel (a) PES spectra for Pt3Mn with partial
appropriate functions to account for the photoemis- contributions of Pt and Mn. In panel (b) the calculated DOS
sion cross-sections and experimental functions. One (Tohyama et al., 1989) (thin solid lines) are properly
example is shown in Figure 2 (Brown et al., 1997). broadened for a meaningful comparison with the
Here, the complete overlap between Pt and Mn d-like experimental data (thick solid line)
sub-bands is indicative of a metallic bond in this
material.
In angle resolved photoemission, the photoelectrons electron final state model; and, when possible, they are
are collected over a small solid angle, and their compared to band structure calculations. This techni-
damping is weak enough that only transitions with k que is labelled ARUPS or ARXPS according to
momentum conservation are involved. Thus, energy whether incident ultraviolet or X-ray photons are
dispersion curves can be probed, which allows one to used; it is applied mainly to single crystals.
investigate band structure topology as well as Fermi In addition to the inner level peaks and to the OB
surfaces. The data are often treated using the free- band, the photoelectron spectra show many satellite
138 Bonding and Stability
Figure 3 Ce 3d PES spectra in a series of Ce(Pd1
xCux)3
intermetallics taken at 1486.6 eV incident energy (Ogawa et
al., 1993)
contributions that may carry important information
about the electronic structure and bonding. They arise
from characteristic energy losses, Auger peaks, shake-
up and shake-off processes, plasmon excitations, sur-
face states, etc. as well as final-state effects. Plasmon
excitations are found towards high EB of the peaks,
whereas surface states give a contribution to the low
EB side. Final-state effects usually do not dominate in
the spectra except for elements with unfilled inner
shells, like the 4f levels of rare earths. Then, the
photoemission spectra show complex features and/or
multiplets involving f n , f nþ1 and f nþ2 final state
configurations (Figure 3) (Ogawa et al., 1993).
In addition to the photoemission peaks that are
superimposed on a background which arises from the
inelastic diffusion of the electrons; for XPS there is an
additional contribution from the Bremsstrahlung
radiation emitted by the X-ray tube. It is often difficult
to account exactly for this background in the OB
range, and models are necessary; however, for core
levels, a linear background can generally be subtracted
from the raw data.
The intrinsic shape of the energy distribution of a
core-level peak is a Lorentzian curve whose full width
at half maximum intensity (FWHM),
En,l, j , depends
on the life time t of the inner hole through:

En,l, j ¼h t
1 ð4Þ
Therefore, core level spectra are usually decomposed
into Lorentzian curves and compared to standards.
Actually, for meaningful decompositions, Voigt func-
tions can also be used, since it is commonly admitted
that the experimental function of the PES spectrometer
is a Gaussian distribution of energy.
The PES core-level spectra bring information from
both qualitative and quantitative standpoints. We
already mentioned that their study may be advanta-
geous for measuring concentration. In addition, they
are very sensitive to the chemical environment; hence
shape modifications (for example, broadenings in
amorphous systems as compared to crystals) as well
as shifts up to a few eV (usually less than 5 eV) with
respect to pure elements can be observed in different
samples. Indeed, the energy of an electron in a core-
level depends on the attractive potential of the nucleus
of the atom and the repulsive interaction due to the
other electrons of the surrounding cloud. As during the
photoemission process, all the orbitals of the system
contribute to the screening of the hole; the screening
energy involves two terms, one is due to the intra-
atomic relaxation of the electronic cloud of the
perturbed atom itself and the other term comes from
the relaxation of neighbour atoms. Therefore, core-
levels are affected by any change of the potentials to
which they are subjected. To account exactly for such
core-level shifts requires reference to models. These
involve relaxation energy terms, electronegativities,
formation enthalpies, etc. Accordingly, investigation
of the chemical shifts in an intermetallic compound is
of great interest, as it brings information on the
chemical state of the probed element. The example of
Figure 4 represents the Al 2p3=2 inner level in fcc Al, an
amorphous intermetallic Al--Cu--Fe and the oxide
present at the surface of the samples. Note that the
feature towards low kinetic energies (high binding
energies) at about 3 eV from the maximum is due to
the contribution of the Cu 3p level to the spectrum of
the intermetallic sample.
 Spectroscopic Approaches
Figure 4 Core-level peak in amorphous Al-Cu-Fe (open
rhombs) and fcc Al (solid line) in the kinetic energy range
around 1404 eV (binding energy around 75 eV). The vertical
bars show the maxima of the Al 2p3/2 peaks in the oxide
(maximum intensity) and the samples and so illustrate
chemical shifts from fcc Al to the amorphous Al-Cu-Fe
alloy (Belin-Ferré, unpublished)
Another interesting piece of information is provided
by examination of the shape of the Fermi edge in
relation to the metallic character of a sample. This
comparison requires measurements with a high energy
resolution; and, accordingly, UPS experiments are
necessary. Many studies have been dedicated to the
investigation of the Fermi edge of intermetallics; in
recent years the presence of a pseudo-gap at EF in
quasicrystalline alloys was verified for icosahedral as
well as decagonal phases which gives indication that
the electronic properties of such alloys depart from
being metal-like. Figure 5 shows the Fermi edges of fcc
Al and Au and icosahedral Al--Cu--Fe and points out a
clear deviation of the OB edge of the icosahedral
intermetallic with respect to what is expected for a free-
electron-like system (Mori et al., 1991).
As mentioned, ARUPS helps to map out the energy
bands of a solid. As an example, we show in Figure 6
the binding energies versus k? for the X direction of
E-FeSi (100) measured between the third and fourth
Brillouin zones and those calculated using a direct
transition model with a free-electron final-state band
139
Figure 5 From bottom to top, experimental Fermi edges
(dots) and calculated Fermi edges (solid lines) for pure gold,
fcc Al and an icosahedral Al-Cu-Fe quasicrystal. For this
latter, the Fermi edge is calculated assuming a free-electron-
like behaviour. The discrepancies between calculation and
experiment demonstrate that the quasicrystal is by no means a
free-electron-like system and emphasizes the low DOS at EF,
therefore establishing the presence of a pseudo-gap
(Castro et al., 1997). The data are compared to band
structure calculations by Mattheis and Hammann
(1993).
Topological investigations are based on the fact that
the photoelectrons are diffracted by the crystal lattice
and therefore carry structural information. Fermi
surfaces are analysed in such a way (Aebi et al.,
1996) as exemplified in Figure 7, which shows the
Fermi surface mappings of Pt (111) and its compar-
ison with theoretical calculations (Pilo et al., 1999a
and b).
In concluding this section, we note that only in very
few cases of ordered alloys, have core-level as well as
140 Bonding and Stability
Figure 6 Experimental binding energies (solid dots) versus
k? for the X direction of E-FeSi (100). The solid lines are the
calculated bands taken from Mattheis and Hammann (1993).
These are shifted by 0.1 eV towards low binding energies for a
better adjustment to the experimental results
Figure 7 Mapping of the Fermi surface of Pt(111) (left side) from PES measurements at room temperature with an incident
radiation of energy 21.2 eV and its comparison with theoretical calculations (right side). Black dots of the calculation are to be
compared with high intensities in the experiment
OB PES photo-diffraction patterns been used to
decompose the OB into the partial densities of states
of its components. We present in Figure 8 the total and
partial DOS of AuCu3 (001) (Stuck et al., 1990).
More information on PES techniques can be found
in many textbooks, such as Barr, 1993; Brundle and
Baker, 1978; Cardona and Ley, 1978 and 1979, or in
Hüfner, 1995, etc.
2.2 X-ray Emission Spectroscopy
An ionized or excited system is not stable and evolves
spontaneously. Therefore, a hole in a core-level of a
solid recombines, radiatively or not, from either a
more external level or the OB. The energy implied in
this recombination is the difference between the
energies of the initial and final states. The initial state
presents a hole in an inner level, and there remains a
more external hole in the final state. The radiative
process is the X-ray emission investigated by X-ray
emission spectroscopy (XES). The non-radiative coun-
terpart is the Auger effect, not treated here, which ends
up emitting electrons and leaving two holes in the final
state. Within the one-electron approximation, thus
neglecting relaxation energy terms, X-ray emission
involves two steps: first, creation of the inner hole at
level Lðn, l, j ) and second, reorganization of the
electronic cloud from another level Lðn0 , l 0 , j 0 ) or from
the OB. This is schematized in Figures 9a and 9b.
The energy distribution of the emitted radiation is
given by
 Spectroscopic Approaches
Figure 8 Partial and total DOS of AuCu3(001) measured in
the (111) direction. Calibration on the DOS scale was made
assuming 10 and 30 electrons/cell for Au and Cu, respectively
IðhnÞ / jMf!i j2 Lðn0 , l 0 , j 0 Þ*Lðn, l, j Þ
or
IðhnÞ / jMf!i j2 NðEÞ*Lðn, l, j Þ
for two levels, Lðn, l, j Þ and Lðn0 , l 0 , j 0 Þ, equation (5),
or for one level and the OB (equation (6)) participating
in the transition, respectively. In equation (6), NðEÞ
denotes the probed OB densities of states. Mf!i is the
matrix element of the transition probability; it is
constant or varies slowly with energy depending on
jh f jrj i ij where i and f are the wave functions of
the initial and final states. Therefore, in equation (5),
the initial and final states are highly localized; in
contrast, in equation (6), i is a localized state whereas
f describes a hole in the OB. Spatial overlapping
between the initial and final wave functions is required
for a transition to take place, and this requirement
implies that only the amplitude of f in the core hole
region will give a significant contribution to the
spectrum. Accordingly, XES has a local character. In
addition, it is necessary that the radiative transition
141
ð5Þ
Figure 9 Sketch of the principle of X-ray emission. Panel a
ð6Þ represents an X-ray transition between two core-levels. Panel
b corresponds to an X-ray emission involving the occupied
band
probability differs from 0, which is achieved provided
the transitions fulfil dipolar selection rules, namely:

l ¼ 1,
j ¼ 0,  1 ð7Þ
As a consequence, if a core hole with symmetry l is
created in an element A, alone or in a compound, the
local density-of-states with l  1 symmetry around this
element, denoted by NðEÞl1 will be probed by the XES
technique, thus giving also a partial character to XES.
Note that (i) transitions with j 0 ¼ 0 ! j ¼ 0 are not
allowed; (ii) transitions to l þ 1 states are favoured
with respect to those to l
1, therefore, from a p hole,
states with d character will be probed with a higher
142 Bonding and Stability
probability than states with s character. Consequently,
comparison of the experimental XES spectra with
partial densities of states calculations is possible. More
details can be found in many textbooks, as for instance
Agarwal (1979), or in Bonnelle (1987).
The shape of the distribution for a transition
involving two inner levels is a Lorentzian curve
whose FWHM is the sum of the FWHMs correspond-
ing to the two levels involved in the transition. The
shape of the emitted intensity distribution to which the
OB contributes results from the convolution of the
probed partial local DOS and the Lorentzian distribu-
tion Lðn, l, j ).
The initial hole can be created either with impinging
electrons or with photons. Irradiation by electrons
easily produces multiple interactions; hence, satellite
emissions due to the X-ray transition in the multiple-
ionized or excited system may also be observed in the
spectra. The XES technique is straightforward, directly
applicable to any kind of material: crystalline, amor-
phous, insulator, bulk, powder, etc. In addition,
according to the conditions of the experimental set-
up it can inform the investigator either with reference
to the bulk sample or to a thin layer just below its
surface. OB of deep interfaces in solids may also be
investigated with XES induced by electrons by tuning
the energy of the incident beam so that it reaches the
depth of the interface in question (Fargues et al., 1985;
Szasz and Kojnok, 1985). The total energy resolution
in an experiment results from the natural width
Eðn,
l, j ) of the inner level Lðn, l, j ) and the instrumental
function.
Eðn, l, j ) varies from a few meV up to
several eV according to the atomic number and
considered level (Krause and Oliver, 1979); and it is
generally the most important parameter in choosing
the appropriate transitions to investigate. Despite the
fact that no absolute DOS values are obtained, it
makes sense to compare the DOS of a given element in
various materials; because, according to equation (6),
any change in the shape and energy of the spectral
distribution will give direct insight into modifications
of the corresponding N(E). An example is given in
Figure 10, which shows the Mg 3p distribution in the
pure metal and in Mg2 CoH5 (Belin et al., 1987). The
feature in the low transition energy range, not present
in the Mg 3p band in the lower curve, corresponds to
additional states due to Mg-H bonding in the
hydrogenated intermetallic.
A relevant characteristic of XES is that the
contributions of the various components to the OB
of a solid can be investigated separately, each one
obtained in its own transition energy scale. To achieve
Figure 10 Mg 3p distribution of states in the pure metal
(lower curve) and in NiMg2H4 (upper curve) on the X-ray
transition energy scale
a picture of the OB and have insight into the electronic
interactions that are present, further adjustment of the
various partial contributions on the energy scale is
necessary. This can be realized on the binding-energy
scale but requires knowing the Fermi energy EF for
each individual X-ray transition energy scale. To do
so, it is necessary to determine the binding energy with
respect to EF of the inner level participating in each X-
ray transition; this can be achieved thanks to
complementary X-ray and (or) inner-level PES mea-
surements. An example is shown in Figure 11 for
Al7 Cu2 Fe. It presents the curves corresponding to the
Al 3p, Al 3s--d, Cu 3d--4s and Fe 3d--4s contributions
to the OB, respectively, as adjusted to the binding
energy scale from the measurements of Al 2p3=2 , Cu
2p3=2 , Fe 2p3=2 inner levels and the X-ray transition Al
2p3=2 ! Al 1s. Each curve is normalized to its own
maximum intensity. Note that as transition probabil-
ities strongly favour d states, no actual view of the Cu
and Fe 4s states is achieved. The overlap between the
peaks for Fe 3d and Al 3p curves denotes a mixing of
the corresponding states and therefore illustrates some
hybridized, covalent character of the Al--Fe bond. The
maximum of the Cu 3d peak is almost at a relative
minimum of the Al 3s--d distribution curve. Here, this
can be interpreted as a Fano-like interaction (Ter-
akura, 1977) between the localized d states and the
extended Al states which splits them into two bonding
and non-bonding parts, located on each side of the Cu
 Spectroscopic Approaches
Figure 11 Al 3s-d (dots), Al 3p (solid line), Cu 3d (stars) and
Fe 3d (triangles) electronic distribution curves in OB of
crystalline Al7Cu2Fe. The full vertical line at the origin
represents the Fermi level, which is located within 0.1 eV for
Al and 0.3 eV for Cu and Fe respectively
Figure 12 Experimental electronic distribution curves
(symbols) and calculated partial DOS’s (solid lines) for
Al7Cu2Fe. From bottom to top, the panels correspond to Cu
d, Fe d, Al p and Al s-d states, respectively. The thick line of the
upper panel is for the Al s states whereas the thin one is for d
states
143
3d maximum (Belin et al., 1992). There is a decrease of
intensity at EF of the various counterparts as
compared to pure metallic elements, which indicates
the opening of a small pseudo-gap at EF in agreement
with the fact that this alloy is a Hume-Rothery
intermetallic.
Comparison between experimental spectra and
partial DOSs is shown in Figure 12 (Trambly de
Laissardière et al., 1995). The agreement is very good
for the Cu and Fe states, but for Al 3p and 3d states
there is a slight discrepancy in the energy range 4 eV
below EF which is still a matter of investigation by
theoreticians (Papaconstantopoulos, 1997). Note that
the features towards low binding energies from the
maximum in the experimental curves of panels a and b
are satellite contributions to the main peak.
The situation is less simple when the sample contains
elements with open shells. The initial state of XES is
then the same as the final state in PES. Therefore many
features are observed on the emission spectral dis-
tribution curves, which arise from final state effects due
to both ionized and excited configurations. Figure 13
displays the Ce 4f--3d emission spectrum of CeNi2 .
Structures due to transitions involving excited and
ionized 3d 9 4f 1 , 3d 10 4f 0 , 3d 9 4f 2 configurations can be
recognized. In this example, the occurrence in the
spectrum of peaks and bumps (arising from peaks of
smaller intensity) characteristic of both Ce3þ and
Ce4þ established that the CeNi2 intermetallic is
actually a mixed valence alloy (Sonder, 1990).
Figure 13 Ce 3d-4f emission spectrum of CeNi2. The two sets
of peaks correspond to transitions involving 3d3/2 and 3d5/2
inner levels, respectively. The bars show the features
characteristic of Ce3+ whereas the arrows show those due
to Ce4+
144 Bonding and Stability
2.3 Complementarity of PES and XES Techniques whereas Ru 5d states (triangles in XES curves) are near
the EF . PES shows that the Cu states are dominant and
As PES provides a view of the total OB and XES gives
also that the total DOS at EF is very low. XES
the partial contributions, it may be interesting to
establishes the low intensity at the EF , especially for
combine both techniques for a better understanding of
the Al states, and shows the interactions between the
the electronic structure of a solid. This is exemplified in
Al and the Cu states on the one hand and between the
Figure 14, which presents the PES and XES OB
Al and Ru states on the other hand. For Ru the energy
spectra of icosahedral quasicrystalline Al--Cu--Ru. For
resolution of XES spectroscopy is not very good,
such an intermetallic, no DOS calculations are
which makes the Ru spectrum broad. The high
available due to the lack of translational properties
resistivity of quasicrystalline Al--Cu--Ru (around
of the quasicrystalline atomic structure. Therefore, it is
1800
cm at room temperature (Berger et al.,
advantageous to investigate the electronic structure
1993)), is in line with the reduced density of the
experimentally. Note that it is of particular interest to
extended-like states, namely Al 3p, in the vicinity of EF
have a view of the Al (or Mg) states and of their
which is about 20% of the intensity in fcc Al, and the
interaction with the other components in such inter-
marked pseudo-gap at EF as assessed from the energy
metallics, since the sp states are less localized in
distance of the Al VB edges from EF .
character than the d states and therefore are more
Another example is shown in Figure 15 for FeSi
sensitive to changes in chemical and topological
where the XPS and XES experimental results are
environments. In addition, they can be principally
involved in many physical and electronic properties;
yet, due to cross-sections that noticeably favour d and f
states, they cannot be recognized in PES spectra.
Figure 14 shows as an example PES curves for
Al65 Cu20 Ru15 (top curve) and Al61:5 Cu25 Ru13:5 (lower
curve) icosahedral quasicrystals; taken from Naka-
mura and Mizutani (1994) and the XES curves for
Al65 Cu20 Ru15 from Belin-Ferré et al. (1996). From
both sets of measurements it appears that Cu 3d states
(crosses in XES spectra) are in the middle of the OB

Figure 15 Electronic structure of FeSi. Top panel: the XPS

Figure 14 PES (XPS) (two upper curves) and XES (four
lower curves) for icosahedral Al–Cu–Ru plotted on the same
energy scale with the vertical line at the origin showing the
Fermi level. All measurements were carried out at room
temperature
spectrum is the dotted line and the total DOS calculated with
the LMTO method is the continuous line. Lower panels: from
top to bottom, the experimental Fe 3d-4s, Fe 4p, Si 3s-d and Si
3p curves are the dotted and broken lines. The partial
calculated DOS are solid lines for Fe 3d, Fe 4p, Si 3s and Si
3p, respectively, and the broken line is for Si 3d (Galakov et
al., 1995)
 Spectroscopic Approaches
compared to total and partial DOS calculations; the
good agreement between the data validates the
theoretical model (Galakov et al., 1995).
3. Investigation of Unoccupied States
3.1 X-ray Photoabsorption Spectroscopy
An incoming photon can deliver its energy to a core
electron (n, l, j ) of a solid and promote it to a normally
unoccupied level, provided the energy of the incident
photon is equal or higher than the ionization thresh-
old. This is schematized in Figure 16. Such a process
leaves an inner hole in the core state. Therefore,
photoabsorption spectroscopy (XAS) and XES can be
considered to be complementary in that, whereas one
spectroscopy refers to occupied states, the other
concerns the unoccupied ones. Similar to XES, in the
one-electron approximation, the energy distribution of
a photoabsorption transition involving the unoccupied
band (UB) results from the convolution between the
energy distributions of the core-level and the conduc-
tion DOS respectively, weighted by the corresponding
transition probabilities.
The spectral energy distribution associated with the
photoabsorption process is
IðhnÞ / jMf!i j2 NðEÞUB *Lðn, l, j Þ ð8Þ
Here also, the photoabsorption transition is expected
to follow the dipole selection rules as expressed in
Figure 16 Sketch of the principle of X-ray photoabsorption
145
equation (7), and its probability depends upon the
overlap between a final state, which may be of
somewhat extended character, and a more localized
initial one. This makes XAS both site and symmetry
selective. Accordingly, the photoabsorption spectrum
describes the sum of all the transitions from the core
level towards continuum states of appropriate angular
momentum. Since the matrix element of the transition
probability is constant or varies very slowly with
energy, XAS spectra are directly related to the
unoccupied DOSs of the solid; but, similar to XES,
no absolute values can be derived from the experi-
ments. Here also, as for XES, the total energy
resolution in an experiment results from the natural
width
Eðn, l, j ) of the inner level Lðn, l, j ) and the
instrumental function.
If I0 is the intensity of the incident photon beam,
and I, the intensity after transmission through a
thickness x of the sample, I and I0 are connected via
the Beer–Lambert law:
I ¼ I0 e
mx ð9Þ
m can be taken as the linear photoabsorption coeffi-
cient since this effect is largely dominant as compared
to others such as the Compton and Thomson
diffusions, Auger emission, etc. m is a function of the
photoabsorption cross-sections, s, of the different
constituents of the solid. Again, the variation of s is
proportional to both i and f , the initial and final
wave functions. i describes the initial state, here the
ground state, and f is the final state, namely the
electron ejected into the UB. Measurements of I and
I0 allow one to determine the variation of m. As a
result of the photoabsorption process, the core-level
vacancy can be filled owing to the Auger process.
Consequently a photocurrent, the so-called photoyield
current Y, is associated with the electrons escaping
from the sample. This current can be measured and
gives rise to the so-called yield technique. The fraction
of the photon intensity absorbed in the sample is
ðI0
I Þ=I0 where I is the photon beam intensity at the
depth x. Therefore, the photoyield current Y can be
written
Y ¼ ðI0
I Þ=I0 ¼ gð1
e
mx Þ ð10Þ
where g is a constant. Because the penetration depth is
much larger than the electron-escaping depth, Y can be
considered to be  gmx. Hence, Y depends on the
mean-free-path of the escaping electrons, and the yield
technique is basically surface-sensitive in contrast to
the transmission technique, which is mainly related to
the bulk material. According to the particular sample,
146 Bonding and Stability
the incident photon beam is totally absorbed through a
thickness x that can vary from tens of nm to mm.
However, the yield technique must be selected when
films a few tens of nm thick, which are often required
for a good experimental accuracy in the transmission
mode, are not available.
To summarize, XAS allows one to investigate partial
local densities of unoccupied states; and, therefore,
comparison with theoretical partial DOSs makes sense.
As for XES, further adjustment of an absolute energy
scale is necessary to reveal a picture of the UB
distribution; and again, measurements of inner-level
binding energies allow one to adjust the various
contributions on the binding energy scale. To exem-
plify, Figure 17a displays the unoccupied electronic
distributions of Al p, Fe d--s and p as well as Cu d--s
and p in Al7 Cu2 Fe (Sadoc et al., 1993); and Figure 17b
shows the partial DOS calculations by Trambly de
Laissardière et al. (1995), broadened in order to
account for the core-level life-time as well as instru-
Figure 17a Experimental empty states distributions in
mental broadenings. Al7Cu2Fe. Solid line: Fe d-s, crosses: Fe p, triangles: Cu d-s,
Similar to XES, qualitative changes in spectral diamonds: Cu p, dots: Al p. All sub-bands are normalized to
shapes from pure elements to intermetallics or from their own maxima. In this alloy, Fe d-s states are
one intermetallic to another one reflect differences in predominantly present at the Fermi level, mainly
bonding due to modifications in charge transfer or overlapping Al p states, whereas Cu d-s states are found
about 2 eV above EF
hybridization. For instance, advantage has been taken
of such a peculiarity to investigate mixed valence
intermetallics and evaluate the valency rates.
By combining both XAS and XES spectra, it is then
possible to have a full view of the electronic distribu-
tions in a solid and a complete derivation of the
electronic interactions. This is exemplified in Figure 18
which shows the experimental OB and UB in icosahe-
dral quasicrystalline Al--Pd--Mn. As the shape of the
Mn UB d-like counterpart is similar to that in the pure
metal (not shown in the figure here), this adjustment
points out that localized states, Mn OB and UB states,
essentially, are found on each side of EF . Accordingly,
there is no significant charge transfer from Al to Mn
states and only a small part of the Al 3p states are
hybridized to Mn 3d states (actually 4s states are not
seen due to transition probabilities that favour d
states). The maxima of Mn and Pd UB states
correspond to relative minima of UB Al p; hence,
this confirms the states are not mixed. Pure Al s OB Figure 17b Theoretical partial DOS in Al7Cu2Fe (Trambly
de Laissardière et al., 1995) broadened to account for the
states are found at about 6 eV below EF . Assuming the core-level life-times involved in the XAS experiments and the
transition probabilities are constant in the investigated instrumental functions. Fe d, Fe s, Cu d, Cu s, Al p, Fe p, and
energy range, the Al p distribution is adjusted to be the Cu p curves are shown. Note that in the calculations, the
same intensity at EF as its OB counterpart. The OB energies are counted opposite in sign to those in the
measurements. Good agreement is found in the energy
and UB Al p-like sub-bands show a marked asym- positions between the experimental curves of Figure 17a and
metry with a minimum at EF which points out the the calculations. Analysis of the shapes shows that empty Fe
formation of a pseudo-gap and a low intensity of the and Cu states are of mixed of d and s characters
 Spectroscopic Approaches 147

Figure 18 OB and UB contributions in an icosahedral Al-Pd-Mn quasicrystal as obtained from XES and XAS experiments,
respectively. Small dots: Al 3s-d, full line: Al 3p, diamonds: Pd 4d-5s, triangles: Mn 3d-4s, large dots: Pd d-s, open dots: Mn d-s,
broken line: Al p. All the curves are normalized to their maximum intensity except for the Al p distribution which, assuming the
transition probabilities are constant, is adjusted to be the same intensity at EF as its OB counterpart

rather extended UB Al p counterpart above EF is
observed. This is in line with the high resistivity of this
intermetallic alloy (about 1000
cm at room tem- selective.
perature at which the spectroscopic measurements are
made) (Belin et al., 1994; Belin-Ferré and Dubois,
1996).
Note that XAS which refers to an energy range of a
few tens of eV above the absorption edges is often
with the energy
labelled as XANES, namely X-ray absorption near-
edge structure in contrast to EXAFS, extended X-ray
absorption fine structures, which is concerned with
energy ranges of a few hundreds of eV above the edges
and mainly carries structural information.
dE / ð1=q2 Þ Imð
1=EÞ ð11Þ
19). Note that as in XAS, there is a remaining core hole
in the final state, therefore this spectroscopy is also site
The energy loss is measured with respect to the
elastic peak in the reflection or the transmission modes
for small scattering angles. The measurements give the
fraction of the incident electron beam with energy E
which is scattered into a solid angle d
from E1 to E1 þ. If we denote by q the momentum
transferred from the incident to the scattered beam,
then the cross-section of EELS is given by:
d2 s=d

3.2 Electron Energy Loss Spectroscopy
A mono-energetic incident electron beam directed into
a solid is slowed down because of collisions, either
elastic or inelastic, with the core electrons. When the
incident energy is high enough, ionizations and
excitations of the electrons of the solid can be
produced, and inner shell electrons can be promoted
to unoccupied states of appropriate symmetry. Thus,
electron energy loss spectroscopy (EELS) allows one to
explore the distribution of unoccupied states (Figure
dE / i,f jh i jqrj f ij2 dðEf
Ei
--
Imð
1=EÞ is the so-called energy loss function and E is
the dielectric constant which is connected to the
photoabsorption coefficient: For energies around
10 eV, the loss function is mainly determined by the
collective excitations of the valence electrons, whereas
for higher energies core excitations are taken into
account. Finally, in the independent particle approx-
imation, and for small momentum transfers,
d2 s=d
hoÞ ð12Þ
148 Bonding and Stability

Figure 20 EELS spectra describing Al s empty states in fcc

Al (upper curve) and in icosahedral quasicrystalline
Al65Cu20Ru15 (lower curve), respectively (Terauchi et al., 1996)
Figure 19 Principle of electron energy loss spectroscopy. The
energy losses are measured with respect to the elastic peak
which is taken as the origin
3.3 Bremsstrahlung Isochromat Spectroscopy
An electron beam which penetrates a solid loses energy
Consequently, EELS is subject to fulfilment of dipole due to its interaction with the strong fields of the
selection rules. In the transmission mode, namely using atoms. As a result, photons are emitted continuously
particles of high incident energy, the spectra are up to a limit which corresponds to the very energy of
equivalent to those measured using transmission the incident electron beam. This is the so-called
photoabsorption, whereas for low energy excitations, Bremsstrahlung radiation (from the German word
the spectra obtained in the reflection mode are for braking radiation) which carries information on
dominated by electron mean-free-path effects and the solid itself. Its detection is therefore of high interest
therefore are essentially surface-sensitive, analogous and gives rise to the Bremsstrahlung spectroscopies.
to yield photoabsorption spectra. Note that when the There are two principal ways to detect the Brems-
incident electron energy is close to that of an strahlung radiation, as schematized in Figures 21a and
absorption edge, extra features may appear on the b. In all cases, the incident electron is high in the
spectra due to non-dipolar transitions. Note also that continuum and is thus considered as a free electron. In
as for XAS, no absolute DOS values are achieved
with EELS measurements, but comparisons between
the same element in various samples is possible as the
shapes of the spectral curves are related to the
unoccupied DOSs (Figure 20).
Features due to such energy losses are commonly
observed in electron scanning transmission microscopy
and are also found in XPS spectra where they generally
give rise to broad peaks corresponding to the high
binding energies of the main lines, so-called plasmon
peaks. In UPS spectra, both surface and volume
plasmons can be detected easily. Investigation of such
plasmon features may provide information about the
nature of the solid, in particular about the free-
electron-like character and number of oscillating Figure 21 Principle of Bremsstrahlung spectroscopy a: in the
electrons (Osterwalder et al., 1990). spectral mode and b: in the isochromate mode
 Spectroscopic Approaches 149
process a, incoming electrons of constant energy are elements and intensity distributions as well as many-
dumped into the unoccupied states and the photons body effects (Speier et al., 1985; Hoekstra et al., 1986;
emitted are scanned according to their energy. Because Sobczack and Auleytner, 1988; Speir et al., 1988).
of energy conservation, their variation depicts the Experimental investigations have been carried out so
variation of the empty states. This is the ‘spectral’ far mainly at synchrotron facilities but also using
mode. In process b, the detection is performed at home-made equipments. Two examples are shown,
constant photon energy by varying the energy of the Figure 22 (Czyzyk et al., 1992) and Figure 23 (Ogawa
incident electron beam; here also, the incident elec- et al., 1993). In the latter, final-state effects due to Ce 4f
trons populate the initially empty band, and the configurations can be recognized.
description of the variation of empty states is made
in the ‘isochromate’ mode.
The latter process is also often denoted as ‘inverse
photoemission’ (IPES); hence, the spectral mode is
generally labelled inappropriately as Bremsstrahlung
isochromate spectroscopy (BIS). In any case, whatever
the detection procedure is, these BIS and/or IPES
spectroscopies describe the totality of the empty states
and do not provide chemical selectivity. However,
comparison with total DOS calculations is meaningful.
In addition, Bremsstrahlung spectroscopies are sur-
face-sensitive, since the mean-free-path of the electrons
governs the depth sampled. Many studies have been
dedicated to analysis of the role of transition matrix

Figure 22 Bremsstrahlung isochromate spectrum of MoNi3.

The upper curve is the raw experimental data, the dotted
curve below is the experimental curve with the inelastic
contribution to the background subtracted. The lowest solid Figure 23 Bremsstrahlung isochromate spectra of
curve is the calculated DOS. Peaks labelled A, C, D, E and Ce(Pd1–xCux)3. Multiplet structure arising from Ce f 1
features F, G, H correspond to both Mo and Ni d states, Mo and f 2 configurations is observable whatever x. The
and Ni p, Ni s, Ni p and to Mo s states and Mo and Ni p second peak above EF is due to both Ce and Pd d
states, respectively states
150 Bonding and Stability
Figure 24 Principle of Bremsstrahlung spectroscopy in the
constant initial state mode
Another type of spectroscopy that involves Brems-
strahlung radiation is the constant initial state
spectroscopy (CIS), in which the initial state is the
fundamental state þ one electron in the conduction
band, and the final state is a core-level hole þ two
electrons in the conduction band, as shown in Figure
24. Therefore, the observed spectra result from the
autoconvolution of the empty DOS. In contrast to
BIS, CIS can involve a deep inner level and so can be
bulk-sensitive.
4. Conclusion
The various spectroscopic techniques introduced in
this paper are only a few among those that can
investigate DOSs of intermetallics. They have been
chosen because they are straightforward, thus giving
direct insight into the DOS, although not providing
absolute DOS values. They are all complementary,
each one revealing a special aspect of DOS. As far as
occupied states are concerned, PES gives a total view
of OB states modulated by cross-sections, but it is
surface-sensitive and charging effects may occur for
insulators and semiconductors. On the other hand,
XES can investigate all partial local occupied electro-
nic distributions in a solid whatever they may be, but
XES is mainly related to the bulk (Figure 14). If one is
interested in empty states descriptions, XAS and EELS
provide partial local electronic distributions that may
Figure 25 Occupied and unoccupied densities of states in
Y(Co1–xAlx)2 investigated with XPS (left side of the figure) and
BIS (right side of the figure), respectively, for different x
concentrations. The vertical line at the origin is set at the
Fermi level, and the curves are each normalized to the total
area
be either bulk or surface-sensitive, whereas BIS
techniques refer to total empty DOSs and are more
likely applicable to the study of the surface. Note that
as XAS is both site- and symmetry-selective, the
combination of BIS and XAS techniques may give
insight, for instance, into the role of the core-hole
effects due to strongly correlated empty levels or to
levels close to the Fermi level. It is also possible to
combine PES and BIS techniques using the same
instrument, therefore within the same accuracy, and
have a view of total occupied and empty DOSs (Figure
25) (Son et al., 1999).
Similarly, in the same spectrometer, under the same
experimental conditions, and hence with the same
broadening, it is possible to analyse selected partial
local occupied and empty DOSs that involve the same
inner level from both XES and XAS measurements,
provided films of suitable thickness are available for
the photoabsorption experiments or the yield techni-
que is used (Figure 18). All parameters that influence
DOS, such as changes due to modifications in atomic
structure or chemical environments can be investigated
and characterized with all these spectroscopic techni-
ques.
Note that other spectroscopic techniques, not
presented here, may also be complementary to one or
more of the techniques described above. For instance,
NMR or Mössbauer spectroscopies can be related to
PES or XES measurements as they both give some
view of the participation of states at EF . See, for
 Spectroscopic Approaches
example, a recent study of the electronic structure of
ion-beam-prepared Al1
x Fex samples which combined
Rutherford back-scattering, conversion electron Möss-
bauer and X-ray emission spectroscopies from which
the metallic character of the compounds was ascer-
tained (Traverse et al., 1996).
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