(A. Goldmann (Auth.), A. Goldmann (Eds.) ) Noble Me PDF

Ref. p. 12] 1.
1 Historical remarks 1
1 Introduction
1.1 Historical remarks
The photoelectric effect has been discovered already in 1887 by Heinrich Hertz [1887H], when he
observed that sparking of a spark gap was enhanced by ultraviolet light. Subsequent work [1888H, 1899T,
1900L, 1902L] revealed that electrons were emitted whose maximum kinetic energy was proportional to
the frequency of the incident light, and whose number was proportional to the light intensity. In 1905
Albert Einstein [1905E] published the quantum theory of the photoelectric effect, for which he received
the Nobel Prize in 1921. Several reviews give an account of the early and the further history of
photoelectron spectroscopy [32H, 77J, 78C1, 82S1, 82S2, 88M]. After more than 100 years since its
discovery, we may state that the photoelectric effect and the many photoelectron spectroscopies based on
it represent one of the most productive areas in solid state and surface science, with considerable impact
also to today's technology.
Modern photoemission spectroscopy, now representing one of the most important tools to investigate
the electronic structures of atoms, molecules, solids and surfaces (including interfaces), started 20 to 30
years ago. Several important experimental developments contributed (among others) to the rapid progress
of that field: The field of X-ray photoelectron spectroscopy (XPS) was pioneered by Kai Siegbahn and his
group, mainly by the development of high-resolution, high-sensitivity electron spectrometers and intense
soft X-ray line-sources (for details see Table 1, Section 1.3) [67S, 69S]. This work was awarded with the
Nobel Prize in 1981 [82S1]. The field of ultraviolet photoelectron spectroscopy (UPS) was pushed
forward mainly by three advances: First, the development of windowless high-intensity uv-lamps such as
the HeI and the HeII line-sources (for details see Table 1, Section 1.3). Second, the advent of high-
resolution, high sensitivity, electrostatic electron energy analyzers which allowed angle-resolved UPS
investigations in reasonable times [82P, 83H, 84C]. Third, the availability of synchrotron radiation from
"dedicated" storage rings as tunable, intense sources of linearly and/or circularly polarized photons [83K].
This instrumental progress allowed to develop experimental methods to measure both the energy and the
momentum of the electrons, i.e. to map the electronic energy band structure along many k-space directions
[82P, 83H, 84C, 92K, 95H1].
For the future we may predict further progress in the field of photoelectron and related spectroscopies.
A new generation of dedicated sychrotron radiation sources is now available. These are based on magnetic
insertion devices (wigglers, undulators) and improved monochromator concepts [97P1]. They supply us
with very intense, high-brilliance radiation of simultaneously high energy-resolution and tunable
polarization. These sources will allow measurements to be performed with photons in the energy range up
to about 1 keV at high photon energy resolution (10...100 meV), high lateral resolution (10...100 nm) and
spectroscopically relevant temporal resolution (pico- to nanoseconds). In conclusion, these sources will
enable us to collect data like those presented in this volume at, however, much improved resolution and
accuracy. This statement refers to core-level spectroscopy as well as to symmetry-resolved mapping of
energy bands.
We may summarize that after more than a century of photoemission studies [95B] the kinematics of
the photoemission process is well understood. This refers to both one-photon photoemission [92K, 95H1]
and two-photon photoemission [95F, 95S]. Provided good quality single-crystals as well as recipes to
prepare surfaces with the desired stoichiometry and sufficient lateral order are available, the determination
of energies and energy bands is now almost routine using tunable photon sources. This business, however,
is only the lower level of every spectroscopy. The higher and more sophisticated level concentrates on
measurement and understanding of line shapes [98H, 98M, 99H, 99V, 00L, 00M] and peak intensities
La nd o lt - Bö r nst e in
New Series III/23C1
2 1.2 Arrangement of data, 1.3 Definition of quantities [Ref. p. 12
[98M, 99M, 01P]. In the last few years photoelectron spectroscopy has progressed to a point [98H, 98P,
99V, 00R], where these quantities are no longer exclusively determined by experimental resolution
constraints, but also by the "intrinsic" quantities like photohole-lifetime [98H, 00C2, 00P, 01G, 01Z, 02G,
02Z] and the lifetime of the excited electron [00C1, 00E, 00P, 02B]. Spoken more generally, the line
shape may give detailed information on the dynamics of the solid as a correlated many-particle system,
including electron-electron [97P3, 00C1, 00E] and electron-phonon [99H, 99P, 99V, 00L, 00R]
interactions. This development opens up a completely new field which recently got additional impetus by
the advent of two-photon photoelectron spectroscopies with time-resolution on the femtosecond scale
[95H2, 96O, 97O, 97P2, 97P3, 97W, 98A, 98K, 00E, 00P]. Moreover, free-electron-lasers with high-
intensity and high-brilliance specifications will be operating in the near future. We may therefore
anticipate further progress in photoelectron and related spectroscopies.
1.2 Arrangement of data
Each chapter has a separate introduction referring to special aspects of the materials under consideration.
Within each chapter the organisation is as follows. First, general data (as far as available) are summarized
on crystal structure, electronic configuration, work functions, plasmon energies, core level binding
energies, valence band critical point energies, and other relevant quantities. Then diagrams are collected
reproducing angle-integrated as well as angle-resolved valence-band and core level spectra, calculated
energy bands and corresponding densities of states, and in particular experimental electron energy
dispersion curves E(k). When considered necessary, also optical spectra and results obtained with other
experimental techniques are shown to supplement the electronic structure information.
Figures and tables within Chaps. 2.9, 2.10 and 2.11 are numbered consecutively through their
subsections.
In the tables of this volume, experimental errors are given in parentheses referring to the last decimal
places. For example 1.23(45) stands for 1.23 ± 0.45 and 9.9(11) stands for 9.9 ± 1.1.
1.3 Definition of quantities
Two features of photoemission spectroscopy (PES) and its time-reversed counterpart, inverse
photoemission spectroscopy (IPES) are of particular interest: First, initial and final state energies of
radiative transitions are directly determined by the experiment. Other methods, e.g. light absorption or
reflection, can in general only determine the energy difference between initial and final state. Second, the
electron momentum !k may be determined in angle-resolved experiments using single-crystal samples.
The schematics of PES and IPES are shown in Fig. 1. PES and IPES can supply information on the
electron energy eigenvalues E(k) and their dependence on the electron wave vector k. As is evident from
Fig. 1, the combination of both techniques can investigate all energy bands below and above the Fermi
level at EF.
New Series III/23C1
Ref. p. 12] 1.3 Definition of quantities 3
Fig. 1. Schematics of photoemission (top) and inverse photoemission

(bottom). The angles of photon (α) and electron (θ) are defined with respect
to the surface normal. The shaded region of the energy band structure is
accessible to the respective technique. Radiative transitions occur between
initial state | i〉 and final state | f〉.
It is not intended here to describe the techniques and theories of PES and IPES in detail, since many
excellent reviewing articles and detailed monographs are available [70T, 72S, 77B, 77I, 78C1, 78C2,
78C3, 78F, 79B, 79C, 80W, 83D, 83S, 83W, 84B, 84D, 85D, 86H, 86S, 87B, 87L, 88S, 95S]. Therefore,
only a very brief overview of the methods will be given. The typical PES [82P, 83H, 84C, 92K, 95H1]
experiment is illustrated in Fig. 1. Photons of energy !ω impinge on the sample. If a photon is absorbed in
an occupied state | i〉, at energy Ei below the Fermi level EF (Ei = 0 at EF), an electron is excited into an
empty state | f〉 at energy Ef. Energy conservation requires Ef − Ei = !ω (The sign convention used in this
volume is summarized in Fig. 2). If Ef > Evac, the energy of the vacuum level, the electron in the excited
state may leave the sample. The emitted electrons are then analyzed with respect to their intensity, kinetic
energy Ek, and other variables of interest like: direction and polarisation of incident light, emission
direction of electrons with respect to incident photon direction and/or with respect to the crystal lattice
coordinates, and (sometimes) the electron spin-polarization [85K, 86F, 94D]. PES gives thus information
on the occupied states below EF and empty states above Evac. Energy conservation states that !ω = Ef − Ei
= Ek + φ − Ei, where φ = Evac − EF is the work function. If φ is known [79H] or measured (the width of the
experimental photoelectron distribution is given by !ω − φ, compare Fig. 3) both Ei and Ef are uniquely
determined. IPES [83D, 83W, 84D, 85D, 86H, 86S, 88S] is illustrated in Fig. 1 (bottom). The electron at
New Series III/23C1
4 1.3 Definition of quantities [Ref. p. 12
Ei = Ek + φ impinges on the crystal, penetrates the surface and enters the previously empty state | i〉 at Ei >
Evac. By emission of a photon, the state at Ei is connected with state | f〉 at Ef ≥ EF = 0. The emitted photon
of energy !ω is registered in an energy-resolving detector [84D, 86H, 86D, 86S]. Again, Ei and Ef are
determined by the kinematics of the experiment.
Fig. 2a. Sign convention for energies in case of Fig. 2b. Sign convention for energies in case of
metallic samples, where the position of EF is clearly semiconductors and/or insulators, where in general the
observed in the photoelectron spectra. If not stated upper valence band edge at EVBM (valence band
otherwise, the energy zero is at EF. In the literature on maximum) is better defined in the experimental spectra
PES, the term "binding energy" is often used, with the than the position of EF. If not stated otherwise, the
convention that | Ei | = Eb ≥ 0. energy zero is at EVBM. In the literature on PES, the
term "binding energy" is often used, with the
convention that | Ei | = Eb ≥ 0.
Most PES experiments measure an electron distribution curve (EDC), i.e. the number I(Ek) of emitted
electrons, see Fig. 3. If !ω is sufficiently large, emission out of core levels is observable. The area of the
corresponding peak (shaded in Fig. 3, and superimposed to a continuous background of inelastically
scattered electrons) is proportional to the number of emitting atoms. Its energy Ei identifies the emitting
element and very often ("chemical shift") also the chemical environment. Emission from occupied valence
states in PES or into empty valence states in IPES yields information on the density of states. In general,
however, even the angle-integrated EDC does not directly reflect the density of states D(Ei), as idealized
in Fig. 3. In the following we will discuss this point for PES in some detail. Angle-integrated PES of bulk
states can transparently be described by a three-step model [68S] (for more refined treatment we refer to
[83H, 84C, 92K, 95H1]): photoexcitation of an electron, travelling of that electron to the surface, and
escape through the surface into the vacuum. Beyond the low-energy cutoff at Evac travelling through the
solid and escape are described by smooth functions of E and will not give rise to structure in I(Ek).
Therefore primarily the photoexcitation process determines the shape of the EDC. For bulk states, where
New Series III/23C1
crystal momentum !k is a quantum number conserved in the reduced zone scheme ("vertical transitions"
in Fig. 1) we then find for the distribution of photoexcited electrons
I(Ek, !ω) ≈ ∑ ∫ d3k |〈f | p | i〉|2 · δ1 . δ2 (1)

i, f
where δ1 = δ{Ef(k) − Ei(k) − !ω} and δ2 = δ{Ef(k) − φ − Ek}, and the k-space integral is to be extended
only over occupied states | i〉. The δ1-function assures energy conservation, while δ2 selects from all
transitions possible with photons of energy !ω only those that are registered by the electron energy
analyser. If we take for the moment the transition matrix element Mfi = 〈f | p | i〉 to be constant, eq. (1)
reduces to the so-called energy distribution of the joint density of states
I (Ek, !ω) ≈ ∑ ∫ d3k · δ1 . δ2 (2)

i, f
Fig. 3. Illustration of the fact that in angle-integrated

PES the density of occupied states D(Ei) is often
approximately reflected in the emitted electron energy
distribution curve I(Ek).
We will then expect that at low photon energies (typically !ω < 20 eV) the angle-integrated EDC does
generally not reflect the density of occupied states, since only few final states for photoexcitation are
available. However, at increasing !ω, the number of accessible final states increases and the intensity
modulation through these | f〉 states becomes less important. The EDC will then progressively become a
replica of the initial density of states (DOS), as long as Mfi = constant. If Mfi is not constant, the EDC
represents the initial DOS modulated by the matrix element varying in k-space. Similar considerations are
applicable to IPES.
The experimental method for mapping Ei(k) is angle-resolved PES, with vacuum-ultraviolet
excitation radiation [82P, 83H, 84C]. While Ei and Ef are easily determined, a problem [82P, 83H, 84C,
92K, 95H1] arises with k. Upon penetration of a single-crystal surface by an electron only k||, the wave-
vector component parallel to the surface, is conserved and directly obtainable from the kinematical
parameters: k|| = sinθ (2m/!2)l/2 Ekl/2, where m is the free electron rest mass. The investigation of bulk
states E (k||, k⊥) requires additional information on k⊥ which is not conserved. In most PES experiments
reasonable assumptions were therefore made (e.g. "free-electron-like", i.e. parabolic final state bands
[82P, 83H, 84C, 92K, 95H1]) to extract k⊥ from one EDC. However, several (albeit time-consuming and
tedious) "absolute" methods may also be applied to determine the full wave-vector (k||, k⊥) experimentally
from at least two ECD's viewing the k-space from different directions. A detailed discussion of such
methods has been presented in [82P, 83H, 84C, 92K, 95H1]. For a most elegant new strategy of band
mapping, which provides full control of the three-dimensional k-vector, see [00S, 01S].
New Series III/23C1
Photoelectric cross sections at 1.5 keV for atomic levels are shown in subvolume a, see Fig. 3 of
section 2.5 (see also Fig. 13 of section 2.8 in subvolume b). Data for other excitation energies can be
found in [81G, 76S]. Calculated partial photoionization cross sections in the energy region 0...1500 eV
are given for all elements Z = 1...103 in [85Y]. A list of line sources commonly used in laboratory PES is
given in Table 1.
Table 1. Commonly used line sources for photoelectron spectroscopy [78C1].
Source Energy Relative Typical intensity at Linewidth

[eV] intensity the sample [meV]
[photons s–1]
He I 21.22 100 1 ⋅ 1012 3

Satellites 23.09, 23.75, 24.05 < 2 each
He II 40.82 20a) 2 ⋅ 1011 17
48.38 2 a)
Satellites 51.0, 52.32, 53. 00 < 1a) each
Ne I 16.85 100 8 ⋅ 1011
16.67
Ne II 26.9 20a)
27.8 10a)
30.5 3 a)
Satellites 34.8, 37.5, 38.0 <2 each
Ar I 11.83 100 6 ⋅ 1011
11.62 80...40a)
Ar II 13.48 16a)
13.30 10a)
Y Mζ 132.3 100 3 ⋅ 1011 450
Mg Kα1, 2 1253.6 100 1 ⋅ 1012 680
Satellites Kα3 1262.1 9
Kα4 1263.7 5
Al Kα1, 2 1486.6 100 1 · 1012 830
Satellites Kα3 1496.3 7
Kα4 1498.3 3
a) Relative intensities of the lines depend on the conditions of the discharge. Values given are therefore only
approximate.
Photoelectron spectroscopies and related or complementary techniques are looking through a

particular surface into the bulk of a solid material. Therefore unavoidably surface and bulk information
are superimposed in the experimental data. Although this volume concentrates on the electronic bulk
properties (for detailed information on the surface electronic and geometric properties see Landolt-
Börnstein III/24a-d) careful inspection of the spectra as well as sufficient understanding of the literature
quoted in this volume require some understanding of the surface as well. To support the reader we
reproduce the relevant bulk and surface Brillouin zones in Figs. 4 - 10.
For further details concerning unit cells, reciprocal lattices and first Brillouin zones see Landolt-Börnstein
III/13c, p.451.
New Series III/23C1
Fig. 4. fcc(100). (Bottom) Bulk Brillouin zone (BBZ) Fig. 5. fcc(110). (Bottom) BBZ and (top) SBZ showing
and (top) Surface Brillouin zone (SBZ) showing the the projection of the bulk onto the (110) surface.
projection of the bulk onto the (001) surface. The bulk
vectors are given by ΓX = [1,0,0] (2π/a), ΓL = [½, ½,
½] (2π/a), ΓK = [¾, ¾, 0] (2π/a), ΓW = [1,½,0] (2π/a)
where a is the lattice constant.
Fig. 6. fcc(111). (Bottom) BBZ and (top) SBZ showing

the projection of the bulk onto the (111) surface.
New Series III/23C1
Fig. 7. bcc(100). (Bottom) BBZ and (top) SBZ

showing the projection of the bulk onto the (001)
surface. The bulk vectors are given by ΓH = [0,0,2]
(π/a), ΓN = [1,1,0] (π/a), ΓP = [1,1,1] (π/a) where a is
the lattice constant.
surface.
←
surface.
New Series III/23C1
Fig. 10. hcp(0001). (Bottom) BBZ and (top) SBZ

surface.
Fig. 11. hcp(1010). (Bottom) BBZ and (top) SBZ

surface.
New Series III/23C1
10 1.4 Frequently used symbols
1.4 Frequently used symbols
Symbol Unit Property
a, b, c Å lattice parameters
DOS eV−1atom−1, density of states
eV−1atom−1spin−1,
atom−1Ry−1
e C elementary charge
E eV, Ry energy
Eb binding energy (Eb ≥ 0)
EF Fermi energy
Ef final state energy (of radiative transition), (Ef ≥ 0)
Eg energy gap, band gap
Ei initial state energy (of radiative transition), (Ei ≤ 0 in
PES, Ei > 0 in IPES), electron incidence energy
Ek kinetic (photoelectron) energy
Evac vacuum energy level
EVBM energy of valence band maximum
∆E eV energy resolution
fi Phillips ionicity
I arb. units, counts s−1 intensity in spectral distribution
k Å−1 wavevector (of electrons)
k||, k⊥ wavevector components parallel and perpendicular
to the surface
kF Fermi surface radius
NOS electrons atom−1 number of states
R reflectivity
T K, °C temperature
Z atomic number
α cm−1 absorption coefficient
α deg angle of incidence of photons in PES, photon
emission angle in IPES
Γ center of Brillouin zone
Γe, Γh inverse life time of electrons, holes
ε2 imaginary part of dielectric constant
q deg angle of incidence of electrons in IPES, electron
emission angle in PES
ν s−1 frequency
hν eV photon energy
σ b cross section
σ s−1 optical conductivity
φ eV work function φ = Evac − EF
ω rad s−1 circular frequency
ωp plasmon frequency
!ω eV photon energy
New Series III/23C1
1.5 List of abbreviations 11
1.5 List of abbreviations
APS appearance potential spectroscopy

APW augmented plane wave (method)
arb arbitrary
ARIPES angle resolved IPES
ARUPS angle resolved ultraviolet photoemission spectroscopy
ASW augmented spherical wave (method)
B, b bulk
bcc body centered cubic
BG background
BIS bremsstrahlung isochromat spectroscopy
BZ Brillouin zone
CIS constant initial state (spectroscopy)
DOS density of states
fcc face centered cubic
FWHM full width at half maximum
hcp hexagonal close packed
IPES inverse photoemission spectroscopy
KKR Kohn-Korringa-Rostoker (method)
KKRZ KKR (method) modified by Ziman
LAPW linearized augmented plane wave method
LCAO linear combination of atomic orbitals
LDA local density approximation
LEED low energy electron diffraction
LEER low-energy electron reflection
LMTO-ASA linearized muffin-tin orbital-atomic sphere approximation
MTO (linear) muffin-tin-orbital (method)
NOS number of states
PE(S) photoemission (spectroscopy)
pol polarized
RAPW relativistic APW
RS-LMTO-ASA real-space LMTO-ASA (method)
RT room temperature
Ry Rydberg (1Ry = 13.605 eV)
S, s surface
SEE secondary electron emission
UHV ultra high vacuum
UPS ultraviolet photoemission spectroscopy
UV ultraviolet
VBM valence band maximum
w.r. with respect
XPS X-ray photoelectron spectroscopy
⊥, || perpendicular, parallel to a crystallographic axis
New Series III/23C1
12 1.6 References for 1
1.6 References for 1
1887H Hertz, H.: Ann. Physik (Wiedemann's) 31 (1887) 983.

1888H Hallwachs, W.: Ann. Physik (Wiedemann's) 33 (1888) 301.
1899T Thomson, J. J.: Philos. Mag. 48 (1899) 547.
1900L Lenard, P.: Ann. Phys. (Leipzig) 2 (1900) 359.
1902L Lenard, P.: Ann. Phys. (Leipzig) 8 (1902) 149.
1905E Einstein, A.: Ann. Phys. (Leipzig) 17 (1905) 132.
32H Hughes, A. L., Du Bridge L. A.: Photoelectric Phenomena. NewYork: Mc Graw Hill, 1932.
67S Siegbahn, K., Nordling, C., Fahlmann, R., Nordberg, R., Hamrin, K., Hedmann, J., Johansson,
G., Bergmark, T., Karlsson, S.-E., Lindgren, I., Lindberg, B.: ESCA, Atomic, molecular and
solid state structure studied by means of electron spectroscopy, Nova Acta Regiae Soc. Sci.
Upsaliensis, Ser. IV Vol. 20, Uppsala, 1967.
68S Spicer, W. E.: Phys. Rev. 112 (1968) 114.
69S Siegbahn, K., Nordling, C., Johansson, G., Hedman, J., Heden, P. F., Hamrin, K., Gelius, U.,
Bergmark, T., Werme, L. O., Manne, R., Baer, Y.: ESCA applied to free molecules.
Amsterdam: North-Holland, 1969.
70T Turner, D. W., Baker, A. D., Baker, C., Brundle, C. R.: Molecular Photoelectron Spectros-
copy. NewYork: Wiley-Interscience, 1970.
72S Shirley, D. A. (ed.): Electron Spectroscopy. Amsterdam: North-Holland, 1972.
76S Scofield, J. H.: J. Electron Spectrosc. Relat. Phenom. 8 (1976) 129.
77B Briggs, D. (ed.): Handbook of X-ray and ultraviolet photoelectron spectroscopy. London:
Heyden, 1977.
77I Ibach, H. (ed.): Electron Spectroscopy for Surface Analysis. Heidelberg: Springer, 1977.
77J Jenkin, J. G., Leckey, R. C. G., Liesegang, J.: J. Electron Spectrosc. Relat. Phenom. 12 (1977) 1.
78C1 Cardona, M., Ley, L. (eds.): Photoemission in Solids I, General Principles, Topics in Applied
Physics, Vol. 26. Berlin: Springer, 1978.
78C2 Cardona, M., Ley, L. (eds.): Photoemission in Solids II, Topics in Applied Physics, Vol. 27.
Berlin: Springer, 1978.
78C3 Caroli, C., Roulet, B., Saint-James, D.: Theory of photoemission, in: Handbook of Surfaces and
Interfaces, Dobrzynski (ed.). New York: Garland, 1978.
78F Feuerbacher, B., Fitton, B., Willis, R. F. (eds.): Photoemission and the electronic properties of
surfaces. New York: Wiley, 1978.
79B Berkowitz, J.: Photoabsorption, photoionization and photoelectron spectroscopy. New York:
Academic Press, 1979.
79C Carlson, T. A.: Photoelectron and Auger spectroscopy. New York: Plenum Press, 1979.
79H Hoelzl, J., Schulte, F. K.: Solid Surface Physics, Springer Tracts in Modern Physics, Vol. 85.
Berlin: Springer, 1979.
80W Williams, R. H., Srivastava, G. P., McGovern, I. T.: Rep. Prog. Phys. 43 (1980) 1357.
81G Goldberg, S. M., Fadley, C. S., Kono, S.: J. Electron Spectrosc. Relat. Phenom. 21 (1981) 285.
82P Plummer, E. W., Eberhardt, W.: Adv. Chem. Phys. 49 (1982) 533.
82S1 Siegbahn, K.: Science 217 (1982) 111 (Nobel prize lecture).
82S2 Spicer, W. E., in: Chemistry and Physics of Solid Surfaces IV, Vanselow, R., Howe, R. (eds.),
Springer Series in Chemical Physics, Vol. 20, Berlin: Springer, 1982.
83D Dose, V.: Prog. Surf. Sci. 13 (1983) 225.
83H Himpsel, F. J.: Adv. Phys. 32 (1983) 1.
83K Koch, E. E. (ed.): Handbook of Synchrotron Radiation. Amsterdam: North-Holland, 1983.
83S Smith, N. V., Himpsel, F. J., in: Handbook on Synchrotron Radiation, Koch, E. E. (ed.).
Amsterdam: North-Holland, 1983, pp 905.
83W Woodruff, D. P., Johnson, P. D., Smith, N. V.: J. Vac. Sci. Technol. A1 (1983) 1104.
New Series III/23C1
1.6 References for 1 13
84B Brundle, C. R., Baker, A. D. (eds.): Electron Spectroscopy, Theory, Techniques and
Applications. Vol. V. New York: Academic Press, 1984; In this series also earlier volumes:
Vol. IV (1980). Vol. III (1979), Vol. II (1978), Vol. I (1977).
84C Courths, R., Hüfner, S.: Phys. Rep. 112 (1984) 53.
84D Dose, V.: J. Phys. Chem. 88 (1984) 1681.
85D Dose, V.: Surf. Sci. Rep. 5 (1985) 337.
85K Kirschner, J.: Polarized Electrons at Surfaces, Berlin: Springer, 1985.
85Y Yeh, J. J., Linau, I.: At. Data and Nucl. Data Tables 32 (1985) 1.
86D Dose, V., Fauster, Th., Schneider, R.: Appl. Phys. A40 (1986) 203.
86F Feder, R. (ed.): Polarized electrons in surface physics, Advanced Series in Surface Science,
Vol. l. Hongkong: World Scientific, 1986.
86H Himpsel, F. J.: Comments Cond. Mat. Phys. 12 (1986) 199.
86S Smith, N. V., Woodruff, D. P.: Prog. Surf. Sci. 21 (1986) 295.
87B Borstel, G., Thörner, G.: Surf. Sci. Rep. 8 (1987) 1.
87L Leckey, R. C. G.: J. Electron Spectrosc. Relat. Phenom. 43 (1987) 183.
88M Margaritondo, G.: Phys. Today (April 1988) 66.
88S Smith, N. V.: Rep. Progr. Physics 51 (1988) 1227.
92K Kevan, S. D. (ed.): Angle-resolved Photoemission. Theory and Current Applications, Studies in
Surface Science and Catalysis, Vol. 74, Amsterdam: Elsevier, 1992.
94D Donath, M.: Surf. Sci. Rep. 20 (1994) 251.
95B Bonzel, H. P., Kleint, Ch.: On the History of Photoemission, Progr. Surf. Sci. 49 (1995) 107.
95F Fauster, Th., Steinmann, W., in: Photonic Probes of Surfaces, Vol. 2 of Electromagnetic
Waves: Recent Developments in Research, Halevi, P. (ed.), Amsterdam: North Holland, 1995,
347.
95H1 Hüfner, S.: Photoelectron Spectroscopy – Principles and Applications, Springer-Series in Solid
State Sciences, Vol. 82, Berlin: Springer, 1995.
95H2 Haight, R.: Surf. Sci. Rep. 21 (1995) 275.
95S Steinmann, W., Fauster, Th.: Two-photon Photoelectron Spectroscopy of Electron States at
Metal Surfaces, in: Laser-spectroscopy and Photochemistry on Metal Surfaces; Dai. H. L., Ho,
W. (eds.), Singapore: World Scientific, 1995, 184.
96O Ogawa, S., Petek, H.: Surf. Sci. 363 (1996) 313.
97O Ogawa, S., Nagano, H., Petek, H.: Phys. Rev. B 55 (1997) 10869.
97P1 Peatmann, W. B.: Gratings, Mirrors and Slits. Beamline Design for Soft X-Ray Synchrotron
Radiation Sources, Amsterdam: Gordon and Breach, 1997.
97P2 Pawlik, S., Bauer, M., Aeschlimann, M.: Surf. Sci. 377-379 (1997) 206.
97P3 Petek, H., Ogawa, S.: Progr. Surf. Sci. 56 (1997) 239.
97W Wolf, M.: Surf. Sci. 377-379 (1997) 343.
98A Aeschlimann, M., Burgermeister, R., Pawlik, S., Bauer, M., Oberli, D., Weber, W.: J. Electron
Spectrosc. Relat. Phenom. 88-91 (1998) 179.
98H Hansen, E. D., Miller, T., Chiang, T.-C.: Phys. Rev. Lett. 80 (1998) 1766.
98K Knoesel, E., Hotzel, A., Wolf, M.: Phys. Rev. B 57 (1998) 12812.
98M Matzdorf, R.: Surf Sci. Rep. 30 (1998) 153.
98P Purdie, D., Hengsberger, M., Garnier, M., Baer, Y.: Surf. Sci. 407 (1998) L671.
99H Hengsberger, M., Frésard, R., Purdie, D., Segovia, P., Baer, Y.: Phys. Rev. B 60 (1999) 10796.
99M Matzdorf, R., Gerlach, A., Goldmann, A., Fluchtmann, M., Braun, J.: Surf. Sci. 421 (1999)
167.
99P Paggel, J. J., Miller, T., Chiang, T.-C.: Phys. Rev. Lett. 83 (1999) 1415.
99V Valla, T., Fedorov, A. V., Johnson, P. D., Hulbert, S. L.: Phys. Rev. Lett. 83 (1999) 2085.
00C1 Campillo, I., Pitarke, J. M., Rubio, A., Echenique, P.: Phys. Rev. B 62 (2000) 1500.
00C2 Campillo, I., Rubio, A., Pitarke, J. M., Goldmann, A., Echenique, P. M.: Phys. Rev. Lett. 85
(2000) 3241.
00E Echenique, P. M., Pitarke, J. M., Chulkov, E. V., Rubio, A.: Chem. Phys. 251 (2000) 1.
New Series III/23C1
14 1.6 References for 1
00L LaShell, S., Jensen, E., Balasubramanian, T.: Phys. Rev. B 61 (2000) 2371.
00M Michalke, T., Gerlach, A., Berge, K., Matzdorf, R., Goldmann, A.: Phys. Rev. B 62 (2000)
10544.
00P Petek, H., Nagano, H., Weida, M. J., Ogawa, S.: Chem. Phys. 251 (2000) 71.
00R Reinert, F., Nicolay, G., Eltner, B., Schmidt, S., Hüfner, S., Probst, U., Bucher, E.: Phys. Rev.
Lett. 85 (2000) 3930.
00S Strocov, V. N., Blaha, P., Starnberg, H. I., Rohlfing, M., Claessen, R., Debever, J.-M.,
Themlin, J.-M.: Phys. Rev. B 61 (2000) 4994.
01G Gerlach, A., Berge, K., Goldmann, A., Campillo, I., Rubio, A., Pitarke, J. M., Echenique, P.
M.: Phys. Rev. B 64 (2001) 085423.
01P Pforte, F., Michalke, T., Gerlach, A., Goldmann, A.: Phys. Rev. B 63 (2001) 115405.
01S Strocov, V. N., Claessen, R., Nicolay, G., Hüfner, S., Kimura, A., Harasawa, A., Shin, S.,
Kakizaki, A., Starnberg, H. I., Nilsson, P. O.: Phys. Rev. B 63 (2001) 205108.
01Z Zhukov, V. P., Aryasetiawan, F., Chulkov, E. V., Gurtubay, I. G., Echenique, P. M.: Phys. Rev.
B 64 (2001) 195122.
02B Berge, K., Gerlach, A., Meister, G., Goldmann, A., Braun J.: Surf. Sci 498 (2002) 1.
02G Gerlach, A., Berge, K., Michalke, T., Goldmann, A., Müller, R., Janowitz, C.: Surf. Sci. 497
(2002) 311.
02Z Zhukov, V. P., Aryasetiawan, F., Chulkov, E. V., Echenique, P. M.: Phys. Rev. B 65 (2002)
115116.
New Series III/23C1
Ref. p. 79] 2.9 Noble metals (Introduction) 15
2 Data
(Chap. 2.1-2.5 see subvolume 23A, 2.6-2.8 see subvolume 23B, 2.12 see subvolume 23C2)
2.9 Noble metals
2.9.1 Introduction
The noble metals have played a central role in the elucidation of the electronic structure of solids, in
particular in the development of angle-resolved photoemission and related experimental techniques, and
they provided a testing ground for our theoretical understanding of non simple elements involving
electronic d-bands. Some of the reasons for this role are of experimental nature: sizable single crystals of
sufficient quality were available, recipes to prepare the low-index surfaces were known and these surfaces
are relatively inert (as compared to other materials) with respect to the residual gas in ultrahigh vacuum
environment. Moreover, the noble metals show clear and intense photoelectron structures which are not
obscured by collective (e.g. plasmon) excitations. Also Cu, Ag and Au represent a series of isostructural
and isoelectronic elements which allow to study the influence of relativistic effects in considerable detail.
Finally the interpretation of the electronic structure is not additionally complicated by magnetic effects.
In particular Cu has been a "drosophila" of photoemission techniques. Significant experimental
progress has been demonstrated first at low-index copper surfaces. Quite early polarization dependent
photoemission results [71G, 76D, 78D1] implied the occurrence of direct, k-conserving transitions and no
significant scattering for a large fraction of those excited electrons which leave the crystal. Systematic
band mapping used copper single crystals [78E, 79K1, 79K2, 79T, 81H1] and presented direct
determinations of the energy-dependent inverse lifetimes Γe(Ef) of a bulk band [78E] and of the photohole
lifetime Γh(Ei) [79T]. Later on a long and fruitful series of investigations started to explore the linewidths
of higher lying final bands, and their damping that makes final state gaps almost disappear and mimics
bands with a nearly-free-electron shape [79H2, 79N, 82G1, 83S]. Much of the pioneering work has been
reviewed in detail elsewhere [84C].
This chapter collects data mainly on energy positions of core levels and band dispersions and presents
representative spectra demonstrating photon-energy dependence and variation with electron emission
angle along high-symmetry (mirror-plane) azimuths. For the interpretation of this material it might be
useful in some cases to use additional sources of information. Therefore we give here some (necessarily
incomplete) listing of references. Comprehensive information on light-polarization effects is found e.g. in
[77H, 78S, 79R, 80E, 81B, 95H, 98G, 99M, 00M, 01P]. The influence of Γh(Ei) and Γe(Ef) on measured
linewidths is discussed in great detail by [92S2, 93S1, 98M1, 00C3, 02B], experimental and calculated
widths are collected in [91G, 94M2, 99P1, 00C3, 00E, 00P1, 01G, 01Z, 02B, 02G, 02Z]. See also [98H].
The influence of experimental parameters like energy-resolution, angular resolution and finite sample
temperature is carefully discussed in [98M1], including many references to earlier work; see also [00K,
00N]. The experimental determination of Fermi surfaces using photoemission techniques is a very recent
development and is described in [94A, 95H, 95Q, 98A]. Two-photon photoemission studies, operating
either in the energy domain or using time-resolved (pulse-probe) techniques down to the femtosecond
scale, have started to explore the dynamics of excited ("hot") electrons [97O, 97P1, 97P2, 97W, 98K,
98P, 00E, 00P1]. However, these results go beyond the scope of the present volume and are therefore not
incorporated systematically in this book.
All data refer to room-temperature samples unless stated differently.
New Ser ies III/23C1
16 2.9 Noble metals (Cu) [Ref. p. 79
2.9.2 Cu (Copper) (Z = 29)
Lattice: fcc, a = 3.61 Å [63W].

Brillouin zones: see section 1.3 of this volume
Electronic configuration: (Ar)3d104s1
Work-function [78C2, 79H4]:
φ (100) = 4.59 eV
φ (110) = 4.48 eV
φ (111) = 4.94 eV
φ (poly) = 4.65 eV
Typical errors are ±0.15 eV.
Table 1. Cu. Core-level binding energies in eV

relative to EF [78C2, 92F, 95H]. Typical scatter
between various sources is ± 0.1 eV.
Level n=2 n=3
ns1/2 1096.7 122.5
np1/2 952.5 77.4
np3/2 932.5 75.2
For core-hole lifetime broadenings see [92F].
Table 2. Cu. Occupied valence bands. Comparison of experimental and theoretical determination of the
symmetry points Γ and X in the BZ. Energy values are given in eV w.r. to EF . Experimental errors are
± 0.03 eV if not explicitly given in parentheses. Symmetries are given in double (single) point group
notation.
Symmetry ARUPS ARUPS ARUPS ARUPS ARUPS Theory
Points [79T] [78D2, 79D] [79K2] [84C] [84E]
Γ8+(12) –2.80 –2.75 –2.85 –2.79 –2.85(10)1) –2.73

Γ7+(25) –3.50 –3.56 –3.65 –3.42 –3.40(10)1) –3.34
Γ8+(25) –3.50 –3.56 –3.65 –3.60 –3.70(10)1) –3.54
Γ6+(1) –8.60 – – – – –8.75
X7+(5) –2.00 –2.05 –2.05 –1.95 –2.032,3) –2.01

X6+(5) – –2.15 – –2.12 – –2.16
X7+(2) –2.30 –2.35 – –2.30 –2.353) –2.33
X7+(3) –4.80 –4.80 –4.50 –4.78 – –4.63
X6+(1) –5.15 –5.20 –5.20 –5.14 – –5.14
1) [89W1]. 2) [83W]. 3) [79H1].
For a detailed comparison of differently calculated Γ and X points see [79K2]. For d-hole lifetimes at Γ,
L and X see [99P2, 00C2, 00P1, 01G, 01Z, 02Z]. See also [01S1] for a band-mapping experiment with
absolute determination of wavevectors.
Ref. p. 79] 2.9 Noble metals (Cu) 17
Table 3. Cu. Occupied valence bands. Comparison of theoretical and experimental energies at K and L.
For details see legend to Table 2.
Symmetry Theory [84E] Experimental (ARUPS)
Points
K5(2) –2.26 –2.15 1,4) , –2.13 6)
K5(4) –2.66 –2.50 4) , –2.66 6)
K5(3) –3.06 –2.95 4) , –3.3 2)
K5(1) –4.24 –4.5 1,2) , –4.40 6)
K5(1) –4.59 –4.60 4) , –4.68 6)
L6– (2') –0.39 –0.9(1) 3), –0.85 5)

L4+,5+(3) –2.21
–2.25 (10) 3,4)
L6+(3) –2.32
L6+(3) –3.41
–3.7 (1) 3,4)
L4+,5+ –3.62
L6+(1) –5.04 –5.15 (10) 6)
1) [78D2]. 2) [79D]. 3) [79K2]. 4) [79T]. 5) [82L]. 6) [84C].
Table 4. Cu. Unoccupied bands of the bulk BZ. Energies of symmetry points are given in eV relative to
EF. Symmetries are given in double (single) group notation.
Symmetry points Theory Theory*) Theory *) Experimental
[63B] [75J] [84E]
Γ(2') 23.3 24.2 23.8 23.7(5) 1) *)

Γ(15) 24.6 26.4 25.8 26.5(5) 1) *)
Γ(25') 28.3 – 28.5 28.5(5) 1)*)
L(1) 3.94 4.1 3.8 4.1 2)

L(2') 21.4 22.2 21.5
21.9 3)*)
L(3') 25.7 23.3 22.7
X6– (4') 2.03 2.02 2.21 2.3(3) 4)

X6+(1) 7.29 7.5 6.74 7.4(4) 5), 7.5(5) 6) , 7.9(2)7)
X6–(5') 13.62
13.4 13.8 13.5(5) 3)*), 13.6 8)
X7–(5') 13.81
X7+(3) 18.5 18.6 18.1 18.1(5) 3)*), 18.6 8)
X6+(1) 20.2 21.7 20.1 19.7(5) 4)
*) Data taken from a figure. See also [01S1].

1) [82J]. 2) [82L]. 3) [84C]. 4) [88A]. 5) [83D]. 6) [84Z]. 7) [79K2]. 8) [79D].
Fermi surface radii (in units of 2π/a): kF [100] = 0.827, kF[110] = 0.743 [82C]. For Fermi surfaces see also
Landolt–Börnstein, New Series, Group III,Vol. 13c (1984), p. 116. For information on the surface
electronic properties see Landolt–Börnstein Vol. III/24b and Vol. III/24d.
Figures for 2.9.2
10 2
Cu
10
3d
3p 2p
1
Cross section σ [Mb]
3s 2s
10−1
3s
10 −2
4s 3d
−3 Fig. 1. Cu. Atomic subshell
10 photoionization cross sections for
photon energies from 0 to 1500 eV
10−4 [85Y].
0 200 400 600 800 1000 1200 1400
Photon energy h ω [eV]
Cu Cu(LMM) L 3VV
335.0
Cu(2p3/2) L3M23M23 L3M23V
486 414.2
479 406.8
L2M 23V
I
395.0 L2VV
315.0
Intensity I (Eb)/Eb
Cu(2p1/2 )
500 450 400 350 300
E b [eV]
Fig. 2. Cu. Overview XPS spectrum.

MgKα The insert shows a blow-up of the
Cu(LMM) Cu(3p) Cu(LMM) Auger-electron spectrum
Cu(3s) Cu [79W1]. Data taken with
(×4)
VB unmonochromatized MgKα radiation.
Eb w.r. to EF.
1000 900 800 700 600 500 400 300 200 100 0
Binding energy E b [eV]
Cu 2p 3/2
2p1/2
Intensity I
Fig. 3. Cu. XPS data showing the

region of the spin-orbit-split 2p core-
19.8
levels taken with unmonochromatized
MgKα radiation [79W1]. Eb w.r. to
EF.
975 965 955 945 935 925
3.8 1.0
Cu Cu
3.4 0.8
Intensity I [arb.units]
0.6
3.0
0.4
2.6
EF
0.2
2.2
0
1.8
90 85 80 75 70 65 −10 −8 −6 −4 −2 0 2 4
Binding energy E b [eV] Initial state energy E i [eV]
Fig. 4. Cu. XPS spectrum of the spin-orbit-split 3p core Fig. 5. Cu. XPS spectrum of the valence band obtained
levels, taken with unmonochromatized MgKα radiation with monochromatized (0.5 eV) AlKα radiation (hν =
(hν = 1254 eV) [73H]. Eb w.r. to EF. 1487 eV) [73H].
Cu Cu
Intensity I
He II (48.4 eV)
Intensity I
He II (40.8 eV)
0
He I
DOS
−6 −4 −2 0 = EF
Initial state energy E i [eV]
Fig. 6. Cu. Photoelectron spectra obtained from

0
polycrystalline samples at different photon energies hν.
Energy resolution ∆E = 80 meV at hν = 40.8 eV and 30
meV at 21.2 eV [77B]. For further experimental data 0 = EF 2 4 6 8 10
Energy E − E F [eV]
taken at hν between 9 eV and 26 eV and a comparison
to theoretical photoemission energy distributions see Fig. 7. Cu. Top: Experimental bremsstrahlung
[75J].
isochromat spectrum (photon energy hν = 1486.7 eV,
total resolution 0.7 eV). Bottom: Calculated density-of-
states. Dashed without broadening, solid line including
broadening to simulate instrumental and lifetime widths
[84S].
Cu Cu
3
0.3
BIS
DOS [states / eV⋅atom]

DOS [states / eV⋅atom]
2
0.2
Intensity I
DOS
1
0.1
DOS
0 0
−10 −5 0 5 10 15 EF 10 20 30 40 50 60 70
Energy E [eV] Energy E [eV]
Fig. 8. Cu. Comparison of experimentally determined Fig. 9. Cu. Bremsstrahlung-isochromat spectrum taken
densities-of-states (solid lines) with theoretical at hν = 1486.7 eV (full circles) and calculated density-
calculations (dashed lines). The left-hand vertical scale of-states (thin line: unbroadened, thick line: broadened
refers to the occupied valence states, while the right- to take experimental resolution and life-time width into
hand scale refers to the empty conduction states [82D]. account). The correspondence of structures in the
measured spectrum with features in the broadened DOS
is indicated. [85S]. See also [92F].
1.0 20
Cu Cu
0.8
15
Dielectric constant ε 2
0.6
Reflectivity R
10
0.4 10 ε 2
5
0.2
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Photon energy h ω [eV] Photon energy h ω [eV]
Fig. 10. Cu. Experimental normal-indicence reflectivity Fig. 11. Cu. Experimental ε2 spectra [81W] obtained
data [81W] obtained from different experiments. For from different experiments. For details and tables of the
details and tables of the "most recommended", data see "most recommended" data see [81W]. See also [85P,
[81W]. See also [85P, 01S2]. For surface optical 01S2].
properties see [00M, 00P1].
-0.039 1
Cu
3 1
1’
EF 1
Energy E [Ry]
1 2’
5 2 1’ 3 1 2
-0.539 12 2
2 1 1 3 2
4
3 3 4
5 3
25’
3 4 3
3 1 31
2’
2’ 1
1
1 1
1
1
-0.939 1
1
Γ ∆ X Z W Q L Λ Γ Σ K
Wavevector k
Fig. 12. Cu. Energy bands along high-symmetry directions of the bulk
Brillouin zone using Chodorow's potential for d-electrons and Slater's
APW method [63B]. See also [75J, 78M] for results of a selfconsistent
nonrelativistic KKR calculation. Symmetries given in single group notation.
Cu
5 + 3
1
2.061 2
1 1 1 2
2’
1 3 3
3 25’
1 3
15 4
3’ 3
2’
4 2’
Energy E [Ry]
1 1
1.061 1 1
3
2’
1
5 1 3 4
5’
1 1
4 1
1 2’ 1
0.061 1 3 1
1 2
EF 4’ 3
5 2’
1’ 24
2 1 3 12
3 3 3
3 25’ 1
1 2’ 1 1
-0.939
1
Γ ∆ X Z W Q L Λ Γ Σ K
Wavevector k
Fig. 13. Cu. Energy bands, showing the continuation of Fig. 12 to higher
energies above EF [63B]. Dashed bands obtained by numerically less
accurate interpolation. See also [75J, 78M] for results of a selfconsistent
nonrelativistic KKR calculation. Symmetries given in single group notation.
28
Cu
24
20
16
Energy E [eV]
12
8
4
EF
0
Fig. 14. Cu. Band structure calculated
−4
by a second-principles method using a
−8 combined interpolation scheme
[81L2].
Γ X W L Γ K,U X
Wavevector k
Cu
5
DOS [electrons/atom⋅eV]
4 1.0
EF
3
L(8)
X(8)
2 W(8) 0.5 Fig. 15. Cu. Density-of-states
L(7) X(7) histogram calculated with the
X(6)
X(9) combined interpolation scheme and
1 the band structure of Fig. 14. High-
(×4) symmetry ciritical-point locations are
0 0 indicated [81L2].
-10 -5 0 5 10 15 20 25
Energy E-EF [eV]
7
Cu
6
5
2 Fig. 16. Cu. Calculated ε2 spectrum (solid line) in

comparison with experimental data (dots). The
1 calculations were performed using a combined
interpolation scheme and include spin-orbit effects and
momentum matrix elements [81L2]. See also [01S2].
0 4 8 12 16 20 24 28
4 6+
Cu
2 6- 6-
EF
0 6-
6
6
7+
Energy E [eV]
4 ++5 + 7 ++
−2 7 6++ 7 4+5 8+ 6
8+ 7 6 6 7+
7 6 7+
7 ++ 7 6+
8 6 +
4 +5 + 4+5 6 8+
7 7+ 7 7+
+
6+ 6 6+
−6
6
6
−8
6+ 6+
5 3+4 5 5 5
−10
Γ ∆ X Z W Q L Λ Γ Σ K SX
Wavevector k
Fig. 17. Cu. Relativistic band structure along high-symmetry directions.
The calculation rests on Kohn-Sham-type relativistic one-particle
equations with a local exchange-correlation potential [84E]. For an
extended-LAPW-based complex band structure calculation see [95K].
For metastable bcc Cu see [02T]. Symmetries given in double group
notation.
5 2’ 2 2 1 2
25’
2’ Cu 3
3 3
3 25’ 3
3
1
1
15 1 3 15
2 1
24 3 2’
2’ 4 3’ 1
1 1
2’
20 1 4 1 1
2’
3 1 1 3
16 5
4
4
1
5’ 5’
2
12 1 1 1
Energy E [eV]
1 4
1 3
8 2’ 1
1
1
3
1 1 1
1 3
4 1
3 3
1 4’ 2 1 4’
EF
0 2’ 1
12 5 5 1’ 2 42 5
2 2 3 3
25’ 1 12 2
−4
2
3 3 3 25’ 1 13
2’ 3 2’ 1 3 3
1 1 1
1
1 1
−8
1 1 1
Γ ∆ X Z W Q L Λ Γ Σ K S X
Wavevector k
Fig. 18. Cu. Scalar-relativistic energy bands. The calculation uses a set
of energy parameters optimized for the energy region above EF and is
based on Kohn-Sham-type relativistic one-particle equations with a
local exchange-correlation potential [84E]. Symmetries given in single
group notation.
X K Σ Γ 7
E F= 0 18 h ω [eV] = 14
EF = 0
Cu
5
2 1 −1
−2

2
12
4
−2
3 25’
−4 1
3 −3
1
1 −4
−6
−5
−8 −6
Cu (110) 1
−10 L Λ Γ ∆ X
1.5 2.0 2.5 Wavevector k
Wavevector k [2π/a] T
Fig. 21. Cu. Temperature dependent energy bands along
Fig. 19. Cu(110). Experimentally determined valence the ΓL and ΓX direction of the bulk Brillouin zone.
bands along the ΓKX line of the bulk Brillouin zone. Experiments: filled circles at 25°C, empty circles at
The full curves correspond to the band structure 400°C from normal emission photoelectron spectra.
calculation of [63B], see also Fig. 12. The height of the Initial states are calculated at 25°C (solid lines) and
data points gives the experimental uncertainty [79T]. 400°C (dot-dashed). Final state bands (dashed at 25°C,
dotted at 400°C) are shifted down in energy by the
photon energy !ω as indicated. Shifts from 25°C to
400°C are exaggerated by a factor of 2.5 to show the
effects more clearly [79K1].
dHvA dHvA
E F= 0
6-(2’) Cu
−1 6(1)
7+ 5(1)
4+,5+ 6(3)
6 + (5)
−2 7(2)
4,5(3) 8+(12)
6+(3) 8 + (12) + Fig. 20. Cu. Compilation of
7(5)7 (2) 5(2)
−3
6+(3) 6(3) 7 + 7+ experimental data for the occupied

6(5) 5(1) 5(4) valence band structure [84C].
4+,5+ 6(1) 8+ (25’) Different symbols reflect results
−4 4,5(3) +
7(2’) 7 + (3) 5(3) 8 (25’) obtained using different experimental
6+(1) techniques and/or by different research
−5 teams, for details see [84C]. The solid
6+ (1)
lines represent the calculated bands of
−6 5(1) [84E], compare also Fig. 17. Band
6(1) 6(1) symmetries are given in double
−7 (single) group notation. See also
[01S1]. For d-hole lifetimes at X, L
−8 and Γ see [99P2, 00C2, 00P1, 01G,
01Z, 02Z]. For a quasiparticle
−9 6+ (1) 6 +(1)
calculation treating self-energy effects
L Γ X K Γ see also [02M].
Wavevector k
400
300
Linewidth (FWHM) [meV ]
Fig. 22. Cu, Ag. Experimental upper

Ag Cu limits for the lifetime width Γh of d-
holes derived from photoelectron
200
linewidths of several bulk band
transitions. The solid-line parabola
starting at EF results from calculation
based on the free-electron-gas model.
100 Data taken from [01G, 02G]. For more
elaborated calculations taking the full
electronic structure into account see
[00C2, 01Z, 02Z].
0
−8 −6 −4 −2 0 = EF
8-(15) 5(1)
6-(15)
25 4,5(3)
4-,5-(3’)
6-(3’) 6(1) 7 -(2’)
6(3) 5(1)
6-(2’) 6(1)
20 6+(1)
Cu
7(2’) 7+(3) 5(4)
7(5)
Energy E [eV]
15 7-(5’) Fig. 23. Cu. Compilation of

experimental data for the unoccupied
6(5) 6-(5’) bands above EF [84C]. Different
(1)6
5(1) symbols reflect results obtained using
10 6(1)
different experimental techniques
and/or by different research teams, for
details see [84C]. The solid lines
6+(1) 5(3)
represent the calculated bands of
5 [84E], see also Fig. 18. Band
6+ (1) symmetries are given in double
6-(4’) 5(1) (single) group notation. For energy
6(1) bands along ΓX up to Ef = 37 eV see
EF = 0 [89W1]. See also [01S1].
L Λ Γ ∆ X S K Σ Γ
Wavevector k
W X K Γ K X K Γ
70
(1) Cu 8 -(15’)
25 (1) Cu(110)
6- (15) 60
7 -(2’)
(1)
(4)
50
20
(4)
Energy E [eV]
(1) 40
Energy E [eV]
15 (4) 30
(1)
(1) (3) 20
10
(1)
(4) 10
(1) (1)
b E F= 0
5 2.0 2.5 3.0 3.5 4.0 4.5
Wavevector k [Å−1]
(3)
(3)
(1) Fig. 25. Cu(110). Final state band along the ΓKX
E F= 0 direction of the bulk Brillouin zone determined
W K Σ Z Γ X S experimentally from angle-resolved photoelectron
Wavevector k spectra. The bridging of a gap at the X-point is clearly
Fig. 24. Cu. Compilation of experimental data for the revealed. For comparison a "nearly-free-electron"
unoccupied bands above EF [86G1]. Different symbols parabola is indicated by the dashed line [85B]. See also
refer to results obtained by absolute photoemission [01S1].
techniques (open circles [84C]), inverse photoemission
(solid squares and vertical arrows [86J]), secondary
electron spectroscopy (triangles [84Z]), low-energy
electron reflection (diamonds [82J]) and de Haas-van
Alphen effect (open square [84C]). Solid lines are
calculated bands [84E]. Band symmetries are given in
double (single) group notation. See also [01S1].
6
Cu
4
2 (111)
Intensity I [10 4 counts/channel]
4
Fig. 26. Cu. Normal-emission
photoelectron spectra taken from the
2 (001) three low-index surfaces at a photon
energy hν = 21.2 eV. The three spectra
are normalized to the same measuring
0 time and indicate the drastic difference
in relative intensities resulting from
1 (110) "gap emission" [95H] in Cu(110) and
0 bulk direct transitions in Cu(111) and
Cu(001) [79C1].
−8 −6 −4 −2 0 = EF
Cu(100)
θ = 35° θ = 75°
30° 70°
25°
65°
S1
20°
60°
Intensity I
Intensity I
15°
55°
10° 50°
5° 45°
0° 40°
−8 −6 −4 −2 0 = EF −8 −6 −4 −2 0 = EF
Initial state energy E i [eV] Initial state energy E i [eV]
Fig. 27. Cu(100) Angle-resolved photoelectron spectra S1) observed next to EF between θ = 50° and 75° result
taken at different polar angles θ along the ΓXWK bulk from a d-like surface state [79H1]. For data taken with
mirror plane. Photon energy hν = 21.2 eV, sample linear-polarized photons at θ = 40° see [83G]. For bulk
temperature T = 50K [93M1]. For further data, taken at transitions observed on a stepped Cu(610) surface see
room temperature, see [79H1]. The sharp peaks (label [98M2].
Cu(100)
θ = 35°
30°
25°
20°
Intensity I
15°
10°
Fig. 28. Cu(100). Angle-resolved photoelectron spectra
taken at different polar angles θ along the ΓXUL bulk
5° mirror plane. Photon energy hν = 21.2 eV, sample
temperature T = 50 K [93M1]. For further data taken at
room temperature see [79H1]. For data taken with
0° linear-polarized photons at hν = 40° see [83G].
−8 −6 −4 −2 0 = EF
Cu(100)
E II Γ XUL
unpol.
T b
E Γ XUL
c
Intensity I
Fig. 29. Cu(100). Two examples showing angle-

E II Γ XWK resolved photoelectron spectra taken with 90%-linearly
d polarized HeI radiation (hν = 21.2 eV): (a)-(c)
measured at polar angle θ = 20° along the ΓXUL bulk
unpol. mirror plane and photon incidence angle α = 20°.
e Results are displayed for p-polarized (a), s-polarized (c)
T and unpolarized (b) light. In (d)-(f) analogous results
E Γ XWK
f are given for the ΓXWK plane, with θ = 20° and α =
60° [83W].
−8 −6 −4 −2 0 = EF
Cu(100)
θ = 80°
θ = 35° S
30° ×4
70°
25° 65°
21°
Intensity I
Intensity I
60°
16° 55°
12° 50°
45°
8°
4° 40°
0° 35° S
−8 −6 −4 −2 0 = EF −8 −6 −4 −2 0 = EF
Fig. 30. Cu(100). Angle-resolved photoelectron spectra taken at different polar angles θ along the ΓXWK bulk mirror
plane. Photon energy hν = 40.8 eV [83W]. Peak S is a d-like surface state.
2.6
Cu(100) 0.24 ∆ 1 upper
2.4 0.20
∆1
Pf i /2m [Ry]
0.16
2.2 X1
0.12
2
2.0 ∆2 0.08 × 0.1
∆5 X3 0.04
1.8 0
X5’ Γ X
1.6 ∆1
Energy E [Ry]
1.4
Pf i /2m [Ry]
0.012 ∆ 1 lower
1.2 X1 0.008
2
0.004
0.7 EF ∆1 X 4’ 0
0.6 Γ X
0.5 ∆2 X5
0.4 X2
0.3 ∆5
0.2 ∆ 2’ X3 Pfi /2m [Ry] ∆5
0.1 X1 0.04
0 ∆1 0.02
2
−0.1 0
Γ X Γ X
Wavevector k Wavevector k
Fig. 31. Cu(100). Band structure (left) and momentum k⊥ for transitions from the initial-state bands indicated
matrix elements |Pfi|2 along the [100] direction of the to final states to the third (fourth) upper band of ∆1-
Brillouin zone. The calculation is based on the symmetry. For ∆1 initial states Pfi || [100], for ∆5 initial
combined interpolation scheme [79S] and refers to states Pfi ⊥ [100]. From [79S]. For a critical discussion
bulk→bulk band transitions. The full (dashed) curves in see [80S].
the panels on the right show the variations of |Pfi|2 with
Cu(100) Cu(100)
h ν [eV]
17 h ν [eV]
16 40
Intensity I
15
Intensity I
35
14
32
13
12 30
11
28
10
25
9
8 22
−5 −4 −3 −2 −1 0 = EF −8 −4 0 = EF
Fig. 32. Cu(100). Normal-emission photoelectron Fig. 33. Cu(100). Normal-emission photoelectron
spectra taken with mixed s/p-polarization at different spectra taken with s-polarized light at different photon
photon energies hν [79K2]. energies hν [89W1].
Cu(100)
Intensity I
Fig. 34. Cu(100). Photoelectron

spectrum taken at T = 35K in normal
emission at a photon energy hν = 40.8
eV. An almost constant background
has been subtracted already. Solid
lines indicate the decomposition into
three Lorentzians, and their sum
[94M2]. For data taken at hν = 48.4
eV see [79C1].
−4.5 −4.0 −3.5 −3.0 −2.5 −2.0
Cu(100) Cu(100)
Γ8 + Γ7 +
Γ8 +
T = 973 K
T = 485 K
Intensity I
T = 793 K
Intensity I
T = 295 K
T = 275 K
T = 77 K
−8 −6 −4 −2 0 = EF
T = 70 K Fig. 36. Cu(100). Temperature-dependent spectra for

normal-emission photo-electrons taken at hν = 66 eV.
Note that inelastic background has been subtracted from
−6 −5 −4 −3 −2 −1 0 = EF
the experimental data [86W1, 87W].
Fig. 35. Cu(100). Temperature dependence of normal-

emission photoelectron spectra taken at hν = 40.8eV.
The spectra result from direct transitions at Γ and show
the corresponding splitting of the d-bands [01G]. See
also [93G, 93M1].
Cu(100)
θ = 29°
θ = 30°
28° 26°
27° 24°
25° 21°
Intensity I
Intensity I
23° 16°
18° 11°
13° 6°
0° 0°
0 = EF 1 2 3 4 5 0 = EF 1 2 3 4 5
Fig. 37. Cu(100). The left panel shows experimentally observed inverse photoelectron spectra (hν = 9.7 eV) at
different polar angles θ along the ΓXWK plane, the right-hand panel shows theoretical spectra calculated on the
basis of a one-step theory [84A]. For surface states see also [85G].
Cu(100) 13.00
12.00 12.75
12.50
11.75
12.25
11.50 12.00
11.25 11.75
11.00 11.50
10.75 11.25
Intensity I
Intensity I
10.50 11.00
10.25 10.75
10.00 10.50
9.75 10.25
9.50 10.00
9.25 9.75
9.00 9.25 9.50
E i [eV]
hν [eV]
−5 −4 −3 −2 −1 0 = EF 0 = EF 1 2 3 4
Fig. 38. Cu(100). Photoemission (left) and inverse photoemission (right) spectra showing the s,p-like ∆1 band
crossing the Fermi level for parallel momentum k|| = 0. Photon energies hν and electron incidence energies Ei are
given as parameters [92H2]. For a discussion of linewidths see [93S1] and [93S2, 94M1, 02B].
For Fig. 39 see next page
-65°
Cu(100) α = 35°
α = 0° -65° S3 -55°
S2
S3
S2 -60° -50°
-45°
-55° -40°
-35°
-50°
-30°
B2
Intensity I
Intensity I
-45° -25°
B4
B4 -20°
-40°
-35° -10°
S1
B2
θ = -30°
θ = 0°
B1 B1
0 = EF 5 10 15 20 25 0 = EF 5 10 15 20 25
α = 75°
S3 -55°
S2 -50°
-45°
-40°
-35°
-30°
Intensity I
-25°
-20°
B3
S1 -10°
θ = 0°
B1
0 = EF 5 10 15 20 25
Energy E [eV]
Fig. 40. Cu(100). Inverse photoemission spectra taken at hν = 9.6 eV and at various polar angles θ of the electrons in
the ΓXUL bulk mirror plane for three photon take-off angles α = 0°, α = 35°, and α = 75°. Transitions into bulk and
surface states are labeled B and S, resp. Data from [92S1], see also [86D, 89F].
Cu(100) Cu(100) α = −20°
0 0°
X 4’ 15°
Intensity I
Intensity I
35°
55°
1 2
−2 0 = EF 2 4 6 75°
Energy E [eV]
Fig. 39. Cu(100). Normal-incidence inverse
photoemission spectrum taken at an electron initial
energy Ei = 14.5 eV. Peaks labeled 1,2 are due to image
potential surface states [92H2]. 0 = EF 2 4 6 8
Energy E [eV]
Fig. 41. Cu(100). Inverse photoelectron spectra taken at
hν = 9.6eV. Electron incidence angle θ = –60° and
photon detection along the ΓXUL bulk mirror plane.
The photon take-off angle α is given as a parameter.
The spectra are normalized to equal amplitude at Ef =
5.7 eV and demonstrate the importance of light-
polarization effects [92S1], see also [89F].
Γ XUL Γ XWK Fig. 42. Cu(100). E(k||) diagram for

X Γ M inverse photoemission spectroscopy
8
along the ΓXUL and ΓXWK bulk
mirror planes at a photon energy of
Cu(100) hν = 9.6 eV [90S]. Calculated bulk
band transitions are shown by open
6 symbols without error bars and locate
emission peaks expected on the basis
of a combined interpolation-scheme
calculation [90S]. Experimental peak
positions resulting from bulk states are
Energy E [eV]
4 generally shown as solid symbols

with error bars. The size of the
symbols indicates the intensity of the
transition. The band gaps of the
projected bulk band structure are
2 shown as grey shaded areas.
Experimentally observed transitions
into surface states are marked as open
symbols with error bars. The
dispersion of the surface states is
0 = EF indicated by solid line parabolas
[90S]; see also [86J, 90L]. Symbols
marked with large squares indicate
1.5 1.0 0.5 0 0.5 1.0 1.5 2.0 data points which have been studied as
Wavevector kII [Å−1] a function of temperature in [90S].

Cu(100)
θ = 0°
Cu(110)
θ = 80°
75° Cu(110)
70°
65°
60° T [°C]= 25
55°
50°
Intensity I
45° 200
40°
35°
Intensity I
30°
400
25°
20° 600
15°
10°
5° 800
0°
−6 −5 −4 −3 −2 −1 0 = EF −7 −6 −5 −4 −3 −2 −1 0 = EF
Fig. 43. Cu(110). Angle-resolved photoelectron spectra Fig. 46. Cu(110). Angle-resolved photoelectron spectra
taken at different polar angles θ along the ΓKWX taken in normal emission at hν = 45 eV with the sample
azimuth of the bulk Brillouin zone. Photon energy hν = at different temperatures [77W]. See also [93G] for a
21.2 eV [81C2]. See also [79H1]. Analogous data taken short review of temperature effects and [93M2] for
along the ΓKLU azimuth are reproduced in [81C1]. further theoretical considerations.
Fig. 44. Cu(110). Normal-emission

photoelectron spectra taken with
linearly-polarized photons at hν = 21.2
eV. Sample temperature T = 130 K,
photon incidence angle α = 45° along
the Γ Y direction of the surface
Brillouin zone. For ease of
10 G comparison, the s-pol spectrum is
Cu(110) shifted vertically by two units of the
9
ordinate scale [98M3]. All transitions
8 labeled A-I are from bulk states
[83B1], while S is a replica of peak G
Intensity I [10 4 counts/3s]
7 induced by a weak satellite line of the

6 F light source. For normal emission
spectra taken with unpolarized
E
5 photons of energies hν = 21.2 eV, 40.8
D
4 B eV and 48.4 eV, see [79C1]. For a
(×5) detailed discussion of the effects of
3 s-pol I linearly-polarized light on normal
S spectra see [82B, 82G2, 83B1, 83P].
2 H
Normal emission intensities obtained
1 p-pol A C for different polarizations at a wide
range of photon energies are reported
0
−7 −6 −5 −4 −3 −2 −1 0 = EF and discussed in [79D]. See also
[85W1] for off-normal results. For
dependence on !ω and T see [01G].
D
Cu(110)
10
E θ = 0°
Temp.coeff. b [10− 4 K −1]

10° experiment
20°
Intensity I
5
30°
40° D
50° theory
60° 0
−8 −6 −4 −2 0 = EF 0° 20° 40° 60°

Initial state energy E i [eV] Emission angle θ
Fig. 45. Cu(110). Left: Angle-resolved photoelectron of peak D as observed experimentally and calculated on
spectra taken at room temperature at different polar the basis of the inverse LEED formalism. The
angles θ in the ΓLUX plane of the bulk Brillouin zone. temperature coefficient b is defined to describe the peak
Photon energy hν = 21.2 eV. All curves are normalized intensity I by the equation lnI = –bT+a [83M].
to the same amplitude. Right: Temperature dependence
Cu(110) Cu(110)
B1 B1 T = 320 K
θ = 49°
410 K
40°
480 K
Intensity I
31°
Intensity I
S3
22° 520 K
13° S1
570 K
8°
S1
0°
0 = EF 2 4 6 8 0 = EF 2 4 6 8
Fig. 47. Cu(110). Inverse photoemission spectra taken Fig. 48. Cu(110). Temperature-dependent intensities of
at hν = 9.7 eV for different electron incidence angles θ bulk (B) and surface (S) peaks observed in inverse
along the ΓKLU bulk mirror plane [86J]. Transitions photoemission spectra taken at θ = 35° along the ΓKLU
into bulk (surface) states are labeled B(S). For effect of bulk mirror plane (hν = 9.7 eV) [86J]. See also [90S].
sample temperature see also [90S].
Cu(110) Cu(110)
θ = 44.5°
T = 195 K
265 K
410 K
Intensity I
545 K
705 K
41°
Intensity I
35.5° B2 S2
30°
B1
24.5° 0 = EF 2 4 6 8
Energy E [eV]
18° S3
Fig. 50. Cu(110). Set of angle-resolved inverse
photoelectron spectra taken at different sample
temperatures. Electron incidence angle θ = –57° along
0 = EF 2 4 6 8
the Γ X azimuth of the surface Brillouin zone.
Energy E [eV]
Photons (hν = 9.7 eV) detected at emission angle α =
Fig. 49. Cu(110). Inverse photoemission spectra taken +55°. The estimated background is indicated by the
at hν = 9.7 eV for different electron incidence angles θ dashed line [89F]. See also [90S].
along the ΓKWX bulk mirror plane [86J]. Transitions
into bulk (surface) states are labeled B(S). For effect of
sample temperature see also [90S].
Cu (110) E i [eV]
32.4
30.4
29.4
28.4
27.4
26.4
Intensity I
24.4
23.3
22.4
21.4
20.4 Fig. 51. Cu(110). Normal-incidence inverse
19.4 photoemission spectra for different electron energies Ei
reflecting bulk band dispersion along the ΓKX direction
of the Brillouin zone [90L].
0 = EF 5 10 15 20 25
Energy E [eV]
ΓKLU Γ KWX
Y Γ X
8
Cu(110)
6
Energy E [eV]
2
Fig. 52. Cu(110). E(k||) diagram for
inverse photoemission spectroscopy
along the ΓKLU and ΓKWX bulk
0 = EF hν = 9.6 eV [90S]. For an explanation
of the various symbols see the caption
of Fig. 42.
1.5 1.0 0.5 0 0.5 1.0 1.5
Wavevector kII [Å−1]
Cu (111)
h ν [eV]
11.5
Intensity I
11.0
10.5
10.0
9.5
9.0 Fig. 53. Cu(111). Normal-emission photoelectron
8.5 spectra taken with p-polarized synchrotron radiation at
8.0 different photon energies hν, showing the dispersion
7.5 with hν of several direct transition bulk emission peaks
7.0 and an s,p-like surface state labeled S [79K2]. See also
6.5 [80S]. For high-resolution normal emission data taken
6.0 at hν = 40.8 eV and hν = 48.4 eV see [79C1].
−6 −4 −2 0 = EF
2.4
Cu(111) 0.24
Λ1 0.20 Λ1 upper
L 2’
Pf i /2m [Ry]
2.2 Λ3 0.16
L 3’
0.12
2.0
2
0.08
1.8 0.04 × 0.1
0
1.6
Pf i /2m [Ry]
Energy E [Ry]
1.4 0.012 Λ1 lower

Λ1 0.008
2
1.2 0.004
0
1.0
L1
0.024
0.5 Λ1 L 2’ Λ3 upper
Pfi /2m [Ry]

EF Λ3
0.4 L3
0.016
0.3 L3
0.2 Λ3 2
L1
0.1 0.008 Λ3 lower
0 Λ1
−0.1 0
Γ L Γ L
Fig. 54. Cu(111). Band structure (left) and momentum show the variation of |Pfi|2 with k⊥ for transitions from
matrix elements |Pfi|2 along the (111) direction of the the initial-state bands indicated to final states in the
Brillouin zone [79S]. The calculation is based on the lower Λ1 band. For the Λ1 initial states Pfi || [111], for
combined interpolation scheme [79S] and refers to Λ3 initial states Pfi ⊥ [111]. From [79S]. For a critical
bulk→bulk band transitions. The panels on the right discussion see [80S]. See also [81H3, 99M, 00M, 01P].
Cu (111)
α = 30°
Intensity I
α = 45°
Fig. 55. Cu(111). Normal-emission photoelectron

spectra excited by p-polarized HeI radiation (hν = 21.2
eV) incident at three different angles α with respect to
the surface normal. Sample temperature T = 180K. The
α = 85°
spectra are normalized to equal maximum peak
amplitude [98M3]. See also [01P].
−6 −4 −2 0 = EF
Cu (111) experiment theory
Intensity I
Intensity I
−7 −6 −5 − 4 −3 −2 −1 0 = EF −7 −6 −5 − 4 −3 −2 −1 0 = EF
Fig. 56. Cu(111). Left: Experimental normal-emission photoelectron spectrum taken with unpolarized HeI radiation
(hν = 21.2 eV). Right: Corresponding spectra calculated within the fully relativistic one-step-model using muffin-tin
potential (triangles) and full-potential (solid line), respectively [98F]. S labels a surface state.
Cu (111)
Cu (111) θ = 40°
θ = − 1.5° 20
3.5°
8.5°
α = 0°
13.5° 15 B
Intensity I [10 3 counts/2s]
C
18.5°
A
23.5° α = 20°
28.5° 10 D
E
Intensity I
33.5°
43.5°
α = 40°
48.5° 5
53.5°
α = 60°
58.5°
63.5° 0
−6 −4 −2 0 = EF
68.5° Initial state energy E i [eV]
73.5°
Fig. 58. Cu(111). Angle-resolved photoelectron spectra
78.5° taken at a polar angle θ = 40° along the ΓLUX plane of
the bulk Brillouin zone with p-polarized HeI-radiation
−4 −3 −2 −1 0 = EF (hν = 21.2 eV) incident at different angles α with
Initial state energy E i [eV] respect to the surface normal. For clarity, spectra are
Fig. 57. Cu(111). Angle-resolved photoelectron spectra shifted by 5 units of ordinate scale against each other.
Sample temperature T = 170 K [98G]. For data taken at
taken at different polar angles θ along the ΓLUX plane
of the bulk Brillouin zone. Photon energy hν = 21.2 eV
θ = 10° see also [82G2].
[79H1]. For further data see also [82G2].
15 100
Cu (111) Cu (111)
25 65
Intensity I [10 3 counts/s]
10
X 7+ hν [eV]
X 6+ S
X 7+ 8.0
5 30 65
Intensity I
7.5
0
−2.8 −2.6 −2.4 −2.2 −2.0 −1.8 −1.6 60
Fig. 59. Cu(111). High-resolution photoelectron
spectrum showing the spin-orbit splitting of d-bands at
7.0
the X-point of the bulk Brillouin zone. S labels a
surface state. Photon energy hν = 21.2 eV, sample −3 −2 −1 0 = EF
temperature T = 105 K, electron emission angle θ = 46° Initial state energy E i [eV]
along the ΓLKL plane, electron energy resolution ∆E =
Fig. 60. Cu(111). Temperature-dependent normal-
20 meV, angle-resolution ∆θ = ±0.4° [96M2]. For a emission photoelectron spectra taken at different photon
discussion on phonon contributions to photohole
energies hν. Thermally induced energy shifts are given
linewidths see [96M1, 98M1, 01G] and references
in meV, solid (dashed) curves refer to a sample
quoted therein.
temperature T = 25°C (400°C) [79K1]. See also [82M].
For one-step-model calculations see also [81L1] and
[96M4, 98M1].
Cu (110) Cu (111)
T = 155 K
300 K
Intensity I
Intensity I
405 K T = 145 K
545 K 290 K
705 K 705 K
10 12 14 16 18 20 10 12 14 16 18 20
Fig. 62. Cu(111), Cu(110). Inverse photoemission incidence at θ = –3°(–45°) within the ΓKLX bulk
spectra for a selected bulk transition observed by mirror plane. Photons (hν = 9.7 eV) are detected at
"triangulation" [95H] on two different surfaces for emission angles θ = 55° (30°) [92S1], see also [90S]. E
various sample temperatures. Left (Right): Electron with respect to EF.
Cu (111) ΓLUX
θ = 0° θ = 50°
exp. exp.
S2
S1
Intensity I
θ = 0° ΓLUX
calc. θ = 50°
calc.
−6 −4 −2 0 −6 −4 −2 0
Fig. 61. Cu(111). Upper panels: experimental angle- 703 K). Lower panels: corresponding one-step-model
resolved photoelectron spectra (hν = 21.2 eV) taken at calculations (thick lines: T = 100 K, thin lines: T = 700
different polar angles θ within the ΓLUX plane of the K). Surface states labeled S1 and S2 are not reproduced
bulk Brillouin zone and at different sample by the bulk band calculation [98M1].
temperatures (thick lines: T = 125 K, thin lines: T =
Γ LKL ΓLUX
M‘ Γ M
8
Cu(111)
6
Energy E [eV]
2
Fig. 63. Cu(111). E(k||) diagram for
inverse photoemission spectroscopy
along the ΓLKL and ΓLUX bulk
0 = EF hν = 9.6 eV [90S]. For an explanation
of the various symbols see the caption
to Fig. 42.
1.5 1.0 0.5 0 0.5 1.0 1.5
−1
Wavevector kII [Å ]
Cu (111)
−−
d2 R
dE2
0.4
0.3 Vi = 1 eV
Reflectivity R
0.2
0.1
0
1.0
Vi = 0.01 eV
Reflectivity R
0.5
0
Γ
Γ2‘ Γ15 Γ25‘
Fig. 64. Cu(111). Bottom: Energy bands along the ΓL-

Wavevector k
direction of the Brillouin zone calculated from a

pseudopotential model [82J]. Middle: Elastic
reflectivity R(E) calculated for small absorption
(imaginary part of the potential Vi = 0.01eV). Top: R(E)
calculated for realistic absorption (Vi = 1 eV) and
corresponding negative second derivative −d2R/dE2
[82J]. Note that E is defined with respect to the vacuum
L level. See also [01S1].
16 18 20 22 24 26
Energy E [eV]
Cu (111)
30
Fig. 65. Cu(111). Left: Energy bands

along the ΓL-direction of the Brillouin
Energy E [eV]
20 zone calculated with an optimized

pseudopotential including an energy
dependent absorption term Vi =
0.05(E−EF) [96S]. Right: Derivative
dR/dE of the elastic reflectivity at
10
normal incidence as observed
experimentally (bold line) and
calculated (thin line) [96S]. Note that
E is defined with respect to the
vacuum level. See also [01S1].
L Im k T Γ Re k T L dR/dE
Ref. p. 79] 2.9 Noble metals (Ag) 43
2.9.3 Ag (Silver) (Z = 47)
Lattice: fcc, a = 4.09 Å [63W]

Electronic configuration: [Kr] 4d105s1
φ (100) = 4.64 eV
φ (110) = 4.52 eV
φ (111) = 4.74 eV
φ (poly) = 4.26 eV
Typical errors are ± 0.15 eV
Table 5. Ag. Core-level binding energies in eV

relative to EF [78C2, 92F, 95H]. Typical scatter
beetween various sources is ± 0.1eV.
Level n=3 n=4

ns1/2 719.1 97.0
np1/2 603.8 63.7
np3/2 573.0 58.3
nd3/2 374.0 –
nd5/2 368.1 –
Table 6. Ag. Occupied valence bands. Comparison of theoretical and experimental determination of the
Γ, X and L points in the BZ. Energy values are given in eV relative to EF. Experimental errors are
typically ± 0.04 eV if not given differently in parentheses. Symmetries are given in double group
notation.
Symmetry Theory Theory Theory Theory ARUPS ARUPS ARUPS
Points [72C] [81J] [83B2] [84E] [85N] [85W3] [89W3]
Γ6+ –7.50 –7.92 –6.63 –7.21 – – –
Γ8+ –5.90 –5.97 –5.82 –6.23 –6.19 –6.15
–4.69
Γ7+ –5.46 –5.49 –5.37 –5.80 –5.76 –5.70
Γ8+ –4.75 –3.69 –4.73 –4.69 –4.95 –4.95 –4.95
X6+ –7.13 –6.54 –7.12 –7.00 –7.35 –7.38 –

X7+ –6.99 –6.22 –7.04 –6.82 –7.00 –7.32 –
X7+ –4.21 –2.93 –4.21 –4.25 –4.20 –4.35 –
X6+ –4.03 –2.64 –4.11 –4.04 – –4.12 –
X7 + –3.73 –2.64 –3.79 –3.71 –3.90 –3.82 –
44 2.9 Noble metals (Ag) [Ref. p. 79
Table 6 (cont.)

Points [72C] [81J] [83B2] [84E] [85N] [85W3] [89W3]
L6+ –6.94 –6.34 –6.85 –6.74 –7.13 – –7.10
L4+ ,5+ –5.99 –5.97 –5.91 –6.28 –6.27 –6.25
–4.76
L6+ –5.53 –5.50 –5.44 –5.74 –5.74 –5.80
L6+ –4.20 –4.20 –4.23 –4.31 – –4.55
–2.87
L4+,5+ –3.97 –4.04 –4.01 –4.06 –4.11 –4.30
L6- –0.16 –0.59 –0.62 –0.03 – –0.20 –
For further data see also [84W1, 85N, 85W3]. For experimental d-hole lifetimes at X see [02G], for
calculations at X, L and Γ see [01Z, 02Z].
Table 7. Ag. Unoccupied bands of the bulk BZ. Energies of symmetry points are given in eV relative to
EF.
Points [72C] [81J] [83B2] [84E] [85N] [85W3] [84R]
Γ7– 16.84 – 17.17 16.98 17.0 17.1(2) –

Γ6– 19.49 – 18.99 19.61 23.0 19.2(4) –
L6+ 3.33 3.79 3.82 3.44 – – 3.8(1)
X6– 2.02 1.70 1.88 2.27 – – 2.1(1)
For further data see [85W3, 99P1, 00L, 00P2].

For Fermi surfaces see Landolt–Börnstein, Vol. III/13c (1984), p. 27.
For information on the surface electronic properties see Landolt–Börnstein Vol III/24b and Vol. III/24d.
Figures for 2.9.3
10 2
Ag
4d
10
1
3d
3p
10−1 4p
3s
4s 4d 4p
10 −2 4s
10−3 5s
10−4
0 200 400 600 800 1000 1200 1400
Fig. 66. Ag. Atomic subshell photoionization cross sections for photon
energies up to 1500 eV [85Y].
10 2 10 2
Ag
Photoionization cross section σ [arb.units]
10
1 10
10−1
10 −2 1
0 50 100 150 200 250 300 350 40 60 80 100 120 140 160 180
a Photon energy h ω [eV] b Photon energy h ω [eV]
Fig. 67. Ag. Calculated (a) atomic 4d-subshell cross section near the Cooper minimum [85Y] and (b) experimental
photoionization cross section for photon energies between 40 and 165 eV. In (b) the open circles are values for atoms
[85K], filled circles with error bars are obtained from poly-crystalline metallic Ag [89K3].
Ag(MNN) M5VV
Ag 901.5 Ag(3d5/2 )
M4VV
M45N1V M45N23V
895.5
992
Ag(MNN)
I
Ag(3d3/2 )
1005 975 945 915 885

Intensity I (E b ) / E b
Eb [eV]
Ag(3p3/2 )
Ag( VB)
Ag(3p1/2 )
Ag(3s) Fig. 68. Ag. Overview XPS spectrum.
Ag(4p)
The insert shows a blow-up of the Ag
Ag(4s)
(MNN) Auger-electron spectrum
MgK α (×4) [79W1]. Data taken with unmono-
chromatized MgKα-radiation.
1000 900 800 700 600 500 400 300 200 100 0
(3d5/2 ) Ag
Ag
(3d3/2 )
Intensity I
Intensity I
DOS
6.00
380 370 360 −9 − 8 −7 − 6 −5 − 4 −3 −2 −1 0 = E F
Fig. 69. Ag. XPS data showing the region of the spin- Fig. 70. Ag. XPS valence band spectrum (dotted) taken
orbit-split 3d core level taken with unmonochromatized with monochromatized (0.5eV) AlKα radiation. The
MgKα radiation [79W1]. solid curve is the corresponding density-of-states curve,
calculated within the combined interpolation scheme
[74S1] and smoothed with a Lorentzian broadening to
account for the experimental resolution [74S2].
Ag Ag
hν [eV] = 1487
150
130
120
Intensity I
He II (40.8eV)
110
Intensity I
100
He I (21.2eV) 90
−9 − 8 −7 − 6 −5 − 4 −3 −2 −1 0 = E F 80
70
Fig. 71. Ag. Photoelectron spectra obtained from
polycrystalline samples at different photon energies hν. 60
Energy resolution ∆E = 80 meV at hν = 40.8 eV and 30 −2
−10 −8 −6 −4
meV at 21.2 eV [77B].
Fig. 72. Ag. Valence band photoemission of

polycrystalline samples taken at different photon
energies hν [76W]. See also [89K3] for an experimental
investigation of the Cooper minimum at hν between 40
and 165 eV.
1.0
Ag Ag
0.8
Intensity I
0.6
Reflectivity R
0.4
DOS
0.2
0 = EF 2 4 6 8 10 0 5 10 15 20 25 30
Energy E [eV] Photon energy hν [eV]
Fig. 73. Ag. Top: Experimental bremsstrahlung Fig. 75. Ag. Experimental normal-incidence reflectivity
isochromat spectrum (photon energy hν = 1486.7 eV, data [81W] obtained from different experiments. For
total resolution 0.7 eV). Bottom: Calculated density-of- details and tables of the "most recommended" data see
states. Dotted line without broadening, solid line [81W]. See also [85P, 01S2].
including broadening to simulate instrumental and
lifetime-widths [84S]. For Fig. 74 see next page
Ag
BIS Fig. 74. Ag. Bremsstrahlung-

isochromat spectrum taken at hν =
1486.7eV (dotted) and calculated
Intensity I
density-of-states (thin line:
DOS
unbroadened, thick line: broadened to
DOS take experimental resolution and life-
time width into account). The
correspondence of structures in the
measured spectrum with features in
the broadened DOS is indicated [85S].
See also [92F].
0 = E F 10 20 30 40 50 60 70 80
Energy E [eV]
10
Ag
8
2 Fig. 76. Ag. Experimental ε2 spectra [81W] obtained

from different experiments. For details and tables of the
"most recommended" data see [81W]. See also [85P,
01S2].
0 5 10 15 20 25 30
Photon energy hν [eV]
24
Ag
20
16
12
Energy E [eV]
8 Fig. 77. Ag. Band structure calculated

by a second-principles method using
4 the combined interpolation scheme.
Spin-orbit coupling and other
0 relativistic corrections are included
[81L2]. See also [74S1] and [83B2].
−4 For a calculation using the relativistic
augmented plane wave method see
−8 [72C].
Γ X W L Γ K,U
Wavevector k
5
6 Ag 1.5
Ag
5 4
4 EF X(11) 1.0
3
3 X(8)
2
2 L(7) X(7)
0.5
X(6) X(9) L(8)
1 1
(×4)
0 0
−10 −5 0 5 10 15 20 25
Energy E − E F [eV] 0 4 8 12 16 20 24
Fig. 78. Ag. Density-of-states histogram calculated with
the combined interpolation scheme and the band Fig. 79. Ag. Calculated ε2 spectrum (solid line) in
structure of Fig. 77. High-symmetry critical-point comparison with experimental data (dots). The
locations are indicated [81L2]. See also [74S2]. calculations were performed using a combined
interpolation scheme and include spin-orbit effects and
momentum matrix elements [81L2]. The corresponding
band structure is shown in Fig. 77. See also [01S2].
Ag
20 15
3 4+5
3’ 4 −+5 −
2’ 1 6 6−
6
6−
15 2’
1
Energy E [eV]
6
10
5
6+
1
0 6−
a 2’ b 6
1
3 + 4+5 4 ++5 +
12 8 6 +
−5 25’ 3 3 7+ 6 6 +
6+ +
1 3 1 8 ++ 6 4+5 4 ++5
1 6 6
Γ Λ L Γ Λ L
Fig. 80. Ag. Band structure calculated along the ΓL direction (a) without and
(b) with spin-orbit interactions [83B2].
6
Ag
Ag
Squared matrix element I π f i I [arb.units]

0.2
0.10
2
2
4
2
0.1
0.05
2
0 0 0
Γ Λ L Γ Λ L
Wavevector k
Wavevector k
Fig. 82. Ag(111). Calculated momentum matrix
Fig. 81. Ag(111). Calculated momentum matrix
elements |πfi|2 as explained in legend to Fig. 81 but now
elements |πfi|2 for bulk band→bulk band transitions in
with the fourth Λ6 band (counted from bottom to top) as
parallel polarization vector A || ΓL. The initial state is
the lowest relativistic Λ6 band (see the right panel in the initial state [83B2]. See also Fig. 81.
Fig. 80). The solid (dashed) curve corresponds to the
final state being the first (second) unoccupied Λ6 bands
(see Fig. 80) [83B2]. See also [80S] for a critical
discussion of the applicability of momentum matrix
elements to photoemission intensities. The units for
|πfi|2 are arbitrary, but identical for Figs. 81-84.
0.036 0.2
Ag Ag
0.032
0.028
2
0.024
2
0.020
0.1
0.016
0.012
0.008
0.004
0 0
Γ Λ L Γ Λ L
Fig. 83. Ag(111). Calculated momentum matrix Fig. 84. Ag(111). Calculated momentum matrix
elements |πfi|2 as explained in legend to Fig. 81 but now
elements |πfi|2 as explained in legend to Fig. 81, but
in perpendicular polarization vector A ⊥ ΓL and the now with perpendicular polarization vector A ⊥ ΓL and
first (lowest) Λ6 band as the initial state [83B2]. See the fourth Λ6 band as initial state [83B2]. See also Fig.
also Fig. 81.
81.
4
Ag 6+
6
6− 6−
2
EF
0 6−
6
−2
Energy E [eV]
7 7+ 7+
7 4++5+4+5
−4 6+ 6+
7+ 6+ 7+
8+ 7 6 6 8+
6
7+ 6 7 6+ 7+
−6 8+ 6 8+
7 7 4++5+ 4+5
7+ 6+ 6 7+ Fig. 85. Ag. Relativistic band structure
6 +
6 6+ 6+ 6+
along high-symmetry directions. The
−8 calculation rests on Kohn-Sham-type
relativistic one-particle equations with
a local exchange-correlation potential
5 3+4 5 5 5 [84E].
−10
Wavevector k
6− 6 7− 7−
7 6 6−
28 7 6
7 ++
7
Ag 6+ 6
6 7+
8 6 7 8+
24 6+ 6 6+ 6+
7 6
6 4 +5+ 4+5
+
8− 4+5 8−
20 6− 4 --+5 - 6−
6
7 7+ 6− 7+
7− 6+ 7− 6+
16 − 6
6
6
Energy E [eV]
7 −
12 7
−
7 −−
6 6 6 6
6
8 7 Fig. 86. Ag. Scalar-relativistic energy
6
6+ 6 6+
7 bands. The calculation uses a set of
4 6+
energy parameters optimized for the
6 6− 6− energy region above EF and is based
EF
−
0 6 on Kohn-Sham-type relativistic one-
6
particle equations with a local
exchange-correlation potential [84E].
−4
For a first-principles relativistic
augmented plane wave (APW)
−8 calculation see [72C]. Symmetries in
5 3+4 5 5 5
double group notation.
Wavevector k
2.0 5 K1
3 W3 2 1 L 1 1 4
Γ25’
Ag 1 1 1
1
3
1 3
2
1.6 3 Γ25’ 1
1 2 1
Γ15 L3
X1 3 Γ15 K1 X1
4 4
1.2 2’ 1 3 1
L 3’ X3
X3
5 1 2
Energy E [Ry]
0.8 1 K4
1 4
X 5’ W2’
1 X 5’
0.4 1 K1 1
4
W1 X
X1 1 3 1 1
1 K1
0 X4’ W3
EF 3 2
L1 K3 3 X
4’
− 0.4 1 X 5 2 1 W 1’ W 1 1 1 L 3 L 2’ 1 K 2 X5 Fig. 87. Ag. Band structure resulting

Γ12 2 1 3 Γ12 1 4 2 K4 2
X2 3 2 3 4 X2 from a nonrelativistic self-consistent,
5 2’ 4 K3 1 X3
2’ 1 Γ25’ 3 3 1K all-electron, local-density-functional
− 0.8 1
Γ1 Γ25’
1 X1 X 3 1 W2’ W3 1 2 L1 L 3 1
Γ1
1 1 K
1 1 X1
calculation [90F]. Symmetries in
Γ ∆ X Z W Q L Λ Γ Σ K,U S X single group notation.
Wavevector k
50
Ag
40
Optical conductivity σ [10 s ]
14 −1
A
30
B
20 Fig. 88. Ag. Optical conductivity. Curve A represents

the calculated interband contribution using the energy
band structure of Fig. 87 and includes calculated
10 momentum matrix elements. Curve B shows the
interband plus the Drude optical conductivity.
Experimental results are reproduced by data points
[90F]. See also [01S2].
0 2 4 6 8 10 12 14 16
dHvA dHvA
EF= 0
6− E F (theory)
−1 Ag
Fig. 89. Ag. Compilation of
experimental data for the occupied
−2 valence band structure [85W3].
Different symbols reflect results

−3 obtained using different experimental
7+ techniques and/or by different research
4++5+
−4 6+ teams, for details see [85W3]. The
8+ 7+
solid lines represent the calculated
6+ 8+
−5 bands of [84E], compare also Fig. 85.
+
6 Band symmetries are given in double
7+
7+
−6 8+ group notation. For further data see
8+
4++5+ also [85N, 89W2, 89W3, 99P1, 00L,
7+
−7 00P2]. For d-hole lifetimes at X, L and
6+
6+ 6+ Γ see [02G, 01Z, 02Z] and Fig. 22.
6+
−8
L Λ Γ ∆ X Σ‘ K Σ Γ
Wavevector k
Γ ∆ Γ Σ Γ K X K Σ Γ
EF= 0 EF= 0
Ag (110) E F (theory) Ag (110)
−1
−2 −2

−3
7+
−4 6+ −4
8+
7+ 8+
−5 8+
+ 7+
7 7+
−6 8+ −6
8+ 8+
7+
−7
6+ 6+
6+
−8 −8
Γ ∆ X S K Σ Γ 2 3 4
Wavevector k Extended zone wavevector k [Å−1]
T
Fig. 90. Ag(110). Band structure along the ΓKXKΓ Fig. 91. Ag(110). Comparison of energy eigenvalues
direction in the extended zone scheme of the bulk E(k⊥) along the ΓKX direction determined from
Brillouin zones. All data points [89C] are obtained from normal-emission photoelectron spectra. Solid lines:
angle-resolved photoemission spectra using final states energy bands obtained by methods using absolute k-
in bulk band gaps ("gap emission method" [95H]). The determination [85W3]. Data points: the "free-electron-
full curves are from a local density calculation [72C] like" final-state band shown in Fig. 93 was exploited to
with the Fermi energy shifted by 0.2 eV as indicated
determine k⊥ from the experimental final state energy
[89C]. See also [02G]. Symmetries in double group
notation. [86G2]. See also [00L, 00P2, 02G].
25
Ag
4 −+ 5 − 8−
20 6−
6− 7− Fig. 92. Ag. Compilation of
−
7−
7 experimental data for the unoccupied
15
Energy E [eV]
6− bands above EF [85W3]. Different

symbols reflect results obtained using
7−
different experimental techniques
10 6− and/or by different research teams, for
details see [85W3]. The solid lines
represent the calculated bands of
6+ [84E], see also Fig. 86. Band
5
symmetries are given in double group
6+ notation. For further data see also
6−
EF= 0 [89W2, 89W3]. See also [00P2].
L Λ Γ ∆ X S K Σ Γ
Wavevector k
25
Ag (100)
Ag(110)
hν =
11.6 eV
20
7 + (1)
11.0
Intensity I
Final state energy E f [eV]
6 + (3) 10.2
15
9.4
7 − (5’)
8.6
10
6 − (5’)
7.8
6 + (1)
7.0 eV
−7 −6 −5 −4 −3 −2 −1 0 = E F
5 Initial state energy E i [eV]
Fig. 94. Ag(100). Normal-emission photoelectron

6 − (4’) spectra taken at different photon energies hν [78H2].
EF= 0 See [78H2] also for photoelectrons (hν = 10.2 eV)
X K Σ Γ emitted at different polar angles θ. See also [97H].
Wavevector k
Fig. 93. Ag(110). Final state bands for normal emission
photoelectrons along the ΓKX direction of the Brillouin
zone. Solid lines: calculated [84E], open circles:
experimental results using methods for absolute k⊥-
determination [85W3]. Dotted and dashed lines: "free-
electron"-parabolas fitted to the calculated bands
[86G2]. Thick solid lines characterize branches of Ag(100)
calculated bands with free-electron-like character
[86G2]. Band symmetries in double (single) group hν = 21.22 eV
notation.
Intensity I
hν = 16.85 eV

spectra taken at different photon energies hν [77R]. For
the temperature-dependence of off-normal spectra along hν = 11.83 eV
ΓXWK see [85M]. See also [97H].
−8 −6 −4 −2 EF= 0
←
Ag(100) Fig. 96. Ag(100). Angle-resolved electron energy
distribution curves measured for normal emission with
different photon energies hν with (full lines) s-polarized
and (broken) s-p-polarized light [89W2]. For effects of
circularly polarized light see [89S].
hν = 45 eV
40 Ag(100)
38
Intensity I
36 hν = 105 eV
34
32 100
Intensity I
30
28 95
27
26 90
25 eV
−10 −8 −6 −4 −2 0 = EF 85
80
Ag(100)
θ = 34°
75 eV
−10 −8 −6 −4 −2 0 = EF
32° Initial state energy E i [eV]
30° Fig. 97. Ag(100). Angle-resolved electron energy

distribution curves measured for normal emission with
different photon energies hν with s-polarized light
28° [89W2].
26°
Intensity I
24°
22°
←
20° Fig. 98. Ag(100). Angle-resolved photoemission
spectra taken at a photon energy hν = 14 eV showing a
s, p-like initial state as it approaches and crosses EF
18° with variation of the polar angle θ along the ΓXUL
azimuth of the Brillouin zone. Sample temperature T =
16° 130 K [92H1]. See also [00P2].
−2 −1 0 = EF
Ag(100) Ag(100)
B3 θ = 50° S2 B2
θ = 50° 47.5°
45°
45°
42.5°
40° 40°
37.5° 37.5°
Intensity I
35° 35°
30°
32.5°
Intensity I
25°
30° 20°
25° 15°
20° 10°
5° B1
15° S1
0°
10°
EF = 0 2 4 6 8
5° Energy E [eV]
B1 S1
0° Fig. 100. Ag(100). Inverse photoemission spectra taken
at hν = 9.5 eV for different electron incidence angles
EF = 0 2 4 6 8 10 12 along the ΓXUL bulk mirror plane. Transitions into
Energy E [eV] bulk (surface) states are labeled B(S) [86A]. See also
[85R]. For an extension to energies up to 33 above EF
Fig. 99. Ag(100). Inverse photoemission spectra taken
at hν = 9.5 eV for different electron incidence angles θ see [86A] and [89K1].
along the ΓXWK bulk mirror plane. Transitions into
bulk (surface) states are labeled B(S) [86A].
Ag (110)
Ag(100) hν =
11.6 eV
11.0
10.2
Intensity I
Intensity I
9.4
8.6
1
7.8
7.0 eV
−2 EF = 0 2 4 6 −7 − 6 −5 − 4 −3 −2 −1 0 = E F
Energy E [eV] Initial state energy E i [eV]
Fig. 101. Ag(100). Normal-incidence inverse Fig. 102. Ag(110). Normal-emission photoelectron
photoemission spectrum taken at an electron energy spectra taken at different photon energies hν [78H2].
Ei = 14.5 eV. The peak labeled 1 is due to an image See [78H2] also for photoelectrons (hν = 10.2 eV) taken
potential surface state [92H2]. at different polar angles θ.
Ag (110) C
hν = 21.22 eV
Ag(110) G F E D B
×5
A
unpol
Γ KLU a
×5
p-pol b
Γ KLU
hν = 16.85 eV
×5
s-pol
Intensity I
Γ KLU CB c
Intensity I
×5 A
s-pol
Γ KWX G F E D
d
×5
p-pol A
hν = 11.83 eV Γ KWX
e
X X6 X 7 X7 X 6 X 7
S G C B A
K
Σ
Γ Γ6 Γ8 Γ7 Γ8
−8 −6 −4 −2 EF= 0 −8 −7 −6 −5 −4
Fig. 103. Ag(110). Normal-emission photoelectron Fig. 104. Ag(110). Angle-resolved normal-emission
spectra taken at different photon energies hν [77R]. photoelectron spectra taken at hν = 21.2 eV with
differently polarized photons: (a) unpolarized (light
incident in the ΓKLU bulk mirror plane), (b) p-pol
(ΓKLU), (c) s-pol (ΓKLU), (d) s-pol (ΓKWX), (e) p-pol
(ΓKWX). Bottom: corresponding band structure and
localization of several direct transitions [82G2]. Energy
is with respect to EF.
Ag (110)
θ = 34°
36.5°
39°
41.5°
Intensity I
44°
46.5°
49°
51.5°
54°
56.5° Fig. 105. Ag(110). Angle-resolved photoelectron
59° spectra taken at hν = 21.2 eV for different polar angles
61.5° θ along the ΓKLU bulk mirror plane [85W3]. For
64° normal emission spectra taken at photon energies hν
between 11eV and 36.7eV see [86G2].
−8 −7 −6 −5 −4 −3
Ag (110)
θ = 58°
α = 79°
69°
59°
49°
Fig. 106. Ag(110). Angle-resolved
Intensity I
36° photoelectron spectra taken at fixed

polar angle θ along the ΓKWX bulk
26° mirror plane with p-polarized NeI-
radiation (hν = 16.8 eV). The variable
16° parameter is the angle α of light
incidence [85W2]. The shaded peak
6° results from a s,p-like initial state with
Σ1 symmetry. Its excitation is for-
− 4° bidden at α = 0. See also [00M, 01P,
02B].
−6 −4 −2 EF = 0
Ag(110) Ag(110)
θ = 60° B5 θ=
50° S3
55° 40°
50° 30°
Intensity I
Intensity I
45° 25°
40° S4 20° S2
B’ 1 B’ 2
35° 15°
S1
30° 10°
S1 B1
0° 5°
EF = 0 2 4 6 8 EF = 0 2 4 6 8
Fig. 107. Ag(110). Inverse photoemission spectra taken Fig. 108. Ag(110). Inverse photoemission spectra taken
at hν = 9.7 eV for different electron incidence angles θ at hν = 9.7 eV for different electron incidence angles θ
along the ΓKWX bulk mirror plane. Transitions into along the ΓKLU bulk mirror plane. Transitions into
bulk (surface) states are labeled B(S) [86A]. bulk (surface) states are labeled B(S) [86A]. For an
extension to energies up to 33 eV above EF see [86A].
Ag (111) Ag (111)
hν = 12 eV
11
Intensity I
10
Intensity I
7 −3 −2 −1 0 = EF
6 Fig. 110. Ag(111). Normal-emission photelectron

spectrum taken at hν = 8 eV with p-polarized light
[97M], see also [96M3]. For similar results on Ag(100)
−8 −6 −4 −2 0 = EF see [97H]. See also [00M, 00N, 01P]. Dotted line:
Initial state energy E i [eV] background.
spectra taken at different photon energies hν. The sharp
peak closest to EF results from a surface state [85N].
Ag (111)
See also [00N].
hν = 21.22 eV
Ag(111) hν = 32 eV
Intensity I
30
hν = 16.85 eV
Intensity I
28
25 eV
hν = 11.83 eV − 15 − 10 −5 0 = EF
spectra taken at different photon energies hν [90E]. The
dispersing peak marked by a vertical dash has a
constant final state energy Ef = 17 eV and results from
−8 −6 −4 −2 EF= 0
secondary electron emission around the Γ7-point (com-
pare Fig. 92), see also [79W2]. For spin-resolved
Fig. 111. Ag(111). Normal-emission photoelectron normal photoemission spectra excited by circularly
spectra taken at different photon energies hν [77R]. polarized synchrotron radiation between hν = 14 eV and
24 eV see [89T].
Ag (111) α = 25°
α = 70°
hν = 25.5 eV
hν = 25.5 eV
24.5 24.5
4 3,2 4 5,6
3,2 5,6
23.5 23.5
23.0 23.0
22.4 22.4
21.9
Intensity I
21.4 21.9
20.4 21.4
19.4 20.4
18.4 19.4
17.3 18.4
1 2 3 16.3 17.3
15.3 1 2 3 16.3
13.3 14.3 15.3
14.3
13.3
12.2 12.2 4,5
11.2 4 5 6 11.2 6
−8 −7 −6 −5 −4 −3 −8 −7 −6 −5 −4 −3
Fig. 113. Ag(111). Normal-emission photoelectron of the resonance-like variation of peak intensities with
spectra taken at different photon energies hν. The light hν see [85W3]. These intensity resonances have also
was p-polarized and incident at angles α = 70° (left been studied using constant initial state spectroscopy in
panel) and α = 25° (right panel) with respect to the [89W3] and in Fig. 114.
surface normal [85W3]. See also [85N]. For an analysis
Ag (111)
hν = 65 eV
hν = 65 eV
60
60
Intensity I
58
Intensity I
58
55
55
50
50
45
45
40
40
35
35
−9 −7 −5 −3 −9 −7 −5 −3
Fig. 115. Ag(111). Normal-emission photoelectron spectra taken at different photon energies hν. Left panel: s-
polarized light, right panel: 25% p-polarized light [89W3]. See also [90E].
Ag (111) T = 196 K
I 2,3 268
4 349
2,3 5,6 447
hν = 28.2 eV 520
659
27.2
18 20 22 24 26 28
26.2 Photon energy hν [eV]
25.2 T = 193 K
I4 260
24.2 337
428
Intensity I
Intensity I
491
601
23.2
22.2
18 20 22 24 26 28
21.2
T = 191 K
20.2 I 5,6 254
327
410
19.2 467
554
18.2 eV
−8 −7 −6 −5 − 4 −3 −2 −1 EF = 0 18 20 22 24 26 28
Initial state energy E i [eV] Photon energy hν [eV]
Fig. 114. Ag(111). Left panel: Normal photoemission results reveal resonance-like maxima which exhibit a
spectra taken at different photon energies hν. Sample at very strong dependence on sample temperature T
T = 180 K. Right panel: constant initial state (CIS) [96M4]. See also [85W3] and [89W2]. For inter-
spectra taken at initial state energies indicated by pretations in terms of final state scattering see [96O].
vertical dotted lines in the left panel [96M4]. The CIS-
Ag (111)
SS
× 40
θ = 0°
× 50
2°
× 20
5°
Intensity I
7°
10° Fig. 116. Ag(111). Angle-resolved photoelectron

spectra taken at different polar angles θ along the
×50
ΓLUX bulk mirror plane. Photon energy hν = 21.2 eV
12.5° [82G2]. SS labels the surface state seen prominent just
at EF in Fig. 110. For results taken at θ = 10° with
15° differently linear-polarized light see [82G2].
−8 −6 −4 −2 EF = 0
Ag (111) Ag (111)
θ = 38°
θ = 20° 36°
34°
22° 33°
24°
26° 32°
27°
30°
28°
28°
26°
29°
24°
30° 22°
Intensity I
31° 20°
32° 18°
33° 17°
Intensity I
34° 16°
35°
36° 15°
37° 14°
38° 12°
40° 10°
41° 8°
42°
43°
6°
44° 5°
45° 4°
46° 2°
48° 0°
50°
52° −8 −4 −2
−6 EF = 0
54°
− 4.5
−5 −4 − 3.5 Fig. 117. Ag(111). Angle-resolved photoelectron
Initial state energy E i [eV] spectra taken at different polar angles θ along the
Fig. 118. Ag(111). Angle-resolved photoelectron ΓLUX bulk mirror plane. Photon energy hν = 16.9 eV
spectra taken at hν = 16.9 eV (NeI-radiation) for (NeI-radiation) [85W3]. For angle dependent spectra
different polar angles θ along the ΓLK bulk mirror taken at hν = 10.2 eV along the ΓKLX bulk mirror
plane [85W3]. plane see [78H2].
Ag(111)
B1 B 1’
θ = 45°
30°
S2
Intensity I
S1
15°
0°
-15° Fig. 119. Ag(111). Inverse photoemission spectra taken

B1 B 1’
at hν = 9.7 eV for different electron incidence angles θ
-30° along the ΓLU bulk mirror plane. Transitions into bulk
(surface) states are labeled B(S) [86A]. For an extension
to energies up to 33eV above EF see [86A]. For earlier
-45°
work see [85M].
EF = 0 2 4 6 8
Energy E [eV]
Ref. p. 79] 2.9 Noble metals (Au) 63
2.9.4 Au (Gold) (Z = 79)
Lattice: fcc, a = 4.08 Å [63W]

Electronic configuration: [Xe] 4f145d106s1
φ (100) = 5.5 eV
φ (110) = 5.4 eV
φ (111) = 5.31 eV
φ (poly) = 5.1 eV
Table 8. Au. Core-level binding energies in eV relative to EF [78C2, 92F, 95H]. Typical scatter between
various sources is ± 0.1 eV.
Level n=4 n=5 n=7

ns1/2 762.1 107.2 –
np1/2 642.7 74.2 –
np3/2 546.3 57.2 –
nd3/2 353.2 – –
nd5/2 335.1 – –
nf5/2 – – 87.7
nf7/2 – – 84.0
The 4f7/2 core-level is an often used and convenient energy-calibration standard at Eb = 83.99(5) eV
[81H2]. For core-hole lifetime broadenings see [92F].
Table 9. Au. Occupied valence bands. Comparison of theoretical and experimental determination of the Γ
and L point in the BZ. Energies are given in eV relative to EF. If not specified, experimental errors are
typically ± 0.15 eV.
Symmetry Theory Theory Theory ARUPS ARUPS ARUPS
Points [71C] [81L2] [84E] [80M] [83B3] [86C]
Γ6+ –9.44 –8.60 –9.01 – – –

Γ8+ –5.65 –5.72 –5.75 –5.90 –6.0 –6.01(2)
Γ7+ –4.34 –4.43 –4.33 –4.45 –4.6 –4.68(5)
Γ8+ –3.29 –3.39 –3.38 –3.55 –3.65 –3.71(2)
L6+ –7.35 –7.24 –7.14 – –7.8(2) –

L4+,5+ –5.82 –5.71 –5.88 – –6.2(2) –6.20(5)
L6+ –4.34 –4.46 –4.52 – –4.9(1) –5.00(5)
L6+ –2.81 –2.71 –3.02 – – –3.2(1)
L4+,5+ –2.10 –2.20 –2.29 – – –2.3(1)
L6– –0.72 –1.27 –0.37 – – –
For further data see also [79C2, 86C, 94W1].
64 2.9 Noble metals (Au) [Ref. p. 79
Table 10. Au. Occupied valence bands. Theoretical and experimental determination of the X points.
Energies are given in eV. relative to EF.
Symmetry Theory Theory Theory ARUPS ARUPS

Points [71C] [81L2] [84E] [84W1]*) [84W2]
X6+ –7.39 –7.46 –7.27 – –

X7+ –7.01 –7.17 –6.89 –7.36(2) –7.5(1)
X7+ –2.77 –2.94 –3.00 –3.03(2) –3.0(1)
X6+ –2.60 –2.62 –2.77 –2.90(2) –2.5(1)
X7+ –1.53 –1.86 –1.72 –1.85(2) –1.8(1)
*) See also [89C].
Table 11. Au. Unoccupied bands of the bulk BZ. Energies of symmetry points are given in eV relative to
EF.
Symmetry Theory Theory Theory *) Experiments
points [71C] [81L2] [84E]
Γ7– 15.58 15.54 15.8 16.0(1) 1), 15.9 2)

Γ6– 18.03 16.84 18.1
18.8(5) 1)
Γ8– 18.03 18.16 19.5
L6+ 3.01 3.68 3.0 3.4(1) 3), 3.6(1) 4)

L6– 14.45 14.84 14.5 –
X 6– 1.47 0.91 1.6 1.9(3) 5)

X 6+ 5.80 5.89 5.8
1) [86C] ARUPS. 2) [82J] LEER. 3) [84M] BIS. 4) [86W2] ARIPES. 5) [92H2] ARIPES.
*) Data taken from a figure.
Fermi surface radii (in units of 2π/a): kF [100] = 0.878, kF [110] = 0.736 [78H4]. For Fermi surfaces see
also Landolt-Börnstein, Vol. III/13c (1984), p. 47.
For information on the surface electronic properties see Landolt-Börnstein Vol. III/24b and Vol. III/24d.
Several authors have studied bulk and surface properties of Cu3Au(100) and Cu3Au(111), both
experimentally and theoretically. For information we refer to [89K2, 93H, 93L1, 93L2, 96L, 99C].
Figures for 2.9.4

10 2
5d Au
10
1 4f
4d
4p
10−1 5d 4s
5p
10 −2
5s
Fig. 120. Au. Atomic subshell
10−3 6s photoionization cross section for
[85Y].
10−4
0 200 400 600 800 1000 1200 1400
10 2
Au
10
10−1
Fig. 121. Au. Atomic 5d-subshell
cross section near the Cooper
minimum [85Y].
10 −2
0 50 100 150 200 250 300 350
Au Au(4f7/2)
Au(4f5/2)
Intensity (Eb)/Eb
I
Au(4d 5/2)
Au(4d3/2)
Au(4p3/2)
Au(4s)
Au(4p1/2 )
AuVB
MgK α Fig. 122. Au. Overview XPS spectrum
Au(5p3/2) taken with unmonochromatized MgKα
radiation [79W1].
1000 900 800 700 600 500 400 300 200 100 0
4f7/2 Au (100)- (1×1)

Au B
S
4f5/2
I
Intensity
I
Intensity
Au (100)- (5 ×20) B S
90 86 82
Fig. 123. Au. XPS spectrum of the 4f spin-orbit split

core-levels taken with monochromatized (0.5eV) AlKα-
radiation [83B4]. For results from gold-55-clusters see
[91Q]. Eb relative to EF.
Au (110)- (2×1)
B
85 84 83
S
Fig. 124. Au(100). Photoemission of the 4f7/2 core level
taken at a photon energy hν = 110 eV on (top) the
I
Intensity
unreconstructed (1x1) and the reconstructed (5x20)

surface. Solid lines: experimental result after
background subtraction. Dashed lines: result of
decomposition into bulk (B) and surface (S)
components, both with a FWHM of 0.35 eV. The
observed surface core level shifts are (top) 0.38 eV and
(bottom) 0.28 eV [81H2]. Eb relative to EF.
85 84 83
Binding energy E b [eV] Au (111)
B
taken at a photon energy hν = 110 eV. Solid line: S
experimental result after background subtraction. Dashed
lines: result of decomposition into bulk (B) and surface (S)
I
Intensity
components, both with a width of 0.35 eV. The observed

surface core level shift is 0.35 eV. [81H2]. Eb relative to EF.
→
taken at a photon energy hν = 110 eV. Solid line:
experimental result after background subtraction.
Dashed lines: result of decomposition into bulk (B) and
surface (S) components, both with a FWHM of 0.35 eV.
The observed surface core level shift is 0.35eV. [81H2].
Eb relative to EF. 85 84 83
hν = 40.8 eV
Au Au
hν = 26.9 eV
Intensity I
Intensity I
hν = 21.2 eV
−9 −8 −7 − 6 −5 − 4 −3 − 2 −1 E F = 0 1
Fig. 127. Au. XPS valence band spectrum [74S2] taken
with monochromatized AlKα radiation (hν = 1486.7 eV,
resolution 0.5eV). −8 −6 −4 −2 EF = 0
Fig. 130. Au. Angle-integrated photoelectron spectra
For Fig. 129 see next page taken at different photon energies hν from
polycrystalline (dashed) and liquid (solid lines) samples
[71E].
15 Au
θ = 70°
θ = 0°
10
b Fig. 128. Au. XPS spectra taken with

5 monochromatized (0.25eV) AlKα
radiation from polycrystalline
0 a
samples, at (a) normal emission and
1.2 (b) at θ = 70° off-normal [78C1].
c
0.8 Using weighting factors from the
0.4
corresponding 4f7/2 core-level
intensities, the spectra could be
decomposed into a surface DOS (c)
4 and a bulk DOS (d) [78C1]. The shift
2 d between the bulk d-band center-of-
gravity (vertical solid line at −4.7 eV)
0 and the corresponding surface value
0.5 eV
(dotted, −4.2 eV) is 0.5 eV. Trace (e)
is a calculated bulk DOS from [74S2].
e For results obtained from gold-55-
clusters see also [91Q].
−8 −6 −4 −2 EF = 0
Au
Intensity I
hν = 40.8 eV
Fig. 129. Au. Photoelectron spectra

obtained from polycrystalline samples
at different photon energies hν.
Energy resolution ∆E = 80 meV at
hν = 21.2 eV
hν = 40.8 eV and 30 meV at 21.2 eV
[77B].
−8 −6 −4 −2 EF = 0
1.0
Au
0.8
0.6
Reflectivity R
0.4
Fig. 131. Au. Experimental normal-
incidence reflectivity data [81W]
obtained from different experiments.
0.2
For details and tables of the "most
recommended" data see [81W]. See
also [85P].
0 5 10 15 20 25 30
8
Au
6
Fig. 132. Au. Experimental ε2 spectra

2
[81W] obtained from different
experiments. For details and tables of
the "most recommended" data see
[81W]. See also [85P, 02S].
0 5 10 15 20 25 30
4.6
4.4
Au
4.2
4.0
3.8
3.6
3.4
3.2
3.0
2.8
2.6
Energy E [Ry]
2.4
2.2
2.0
1.8
1.6 Fig. 133. Au. Energy band structure
1.4 calculated using the relativistic
1.2 augmented-plane-wave (APW) method
1.0 [76C]. The variation with temperature
0.8 EF (simulated by calculations at different
0.6 lattice constant a) has been investi-
0.4 8+ 7+
gated in [79C2]. Symmetries in double
0.2 8+
0 group notation.
6+ ∆ Z Q Λ Σ S
− 0.2
Γ X W L Γ K,U X
Wavevector k
24 Au
20
16
12
Energy E [eV]
0
Fig. 134. Au. Band structure
calculated by a second-principles
−4
method using a combined inter-
−8 polation scheme [81L2].
Γ X W L Γ K,U X
Wavevector k
Au L(8) L(9)
4 1.0
X(8)
DOS [electrons/atom ⋅ eV ]
DOS [electrons/atom ⋅ eV ]
3
L(7) Γ(9)
X(7)W(9) X(9)
2 0.5
EF Fig. 135. Au. Density-of-states
histogram calculated with the com-
(×4)
1 bined interpolation scheme and the
band structure of Fig. 134. High-
symmetry critical-point locations are
0
indicated [81L2].
−10 −5 0 5 10 15 20 25
Energy E - E F [eV]
Au
6
0 2 4 6 8 10 12 14 16 18 20 22 24
Fig. 136. Au. Calculated ε2 spectrum (solid line) in
comparison with experimental data (dots). The
calculations were performed using a combined
interpolation scheme and include spin-orbit effects
and momentum matrix elements [81L2].
4
Au 6+
6
2 6- 6-
EF
0 6-
6
7+ 6
Energy E [eV]
−2 7+
7 4 ++5 +
7 6+ 6+
6+ 4+5
8+ 7+ 7+
6 8+
−4 7+ 7+
7 6+ 6
6 7 +
4 +5 + 6
8+ 6 8+
−6 7 7
4+5
7+ 7+
6+ 6+ 6+
−8 6 6
6+ 6+
−10 5 3+4 5 5 5
Wavevector k
Fig. 137. Au. Relativistic band structure along high-symmetry
directions. The calculation rests on Kohn-Sham-type relativistic one-
particle equations with a local exchange-correlation potential [84E].
Symmetries in double group notation.
7+ 7 6 7+
28 8+ 6 7 7- 6 6 8+ 7-
6-
6+ 6-
6
Au 7
6+
4+5
24 6
6+ 7 4 ++5 + 6+
6 6
4+5
20 8- 7 7+ 4 −+5 − 8- 7+
6- 6 6-
6 6+ 6- 6+
16 7- 6 7-
6-
7
Energy E [eV]
12 7- 7-
6
6 6- 6-
7
8 6
6
6+ 7 6+
6
4
6+
EF 6 6- 6-
0 6-
Fig. 138. Au. Relativistic energy
bands. The calculation uses a set of
−4
energy parameters optimized for the
energy region above EF [84E]. See
−8
5 3+4 5 5 5 also Fig. 137. Symmetries in double
Γ ∆ X Z W Q L Λ Γ Σ K S X group notation.
Wavevector k
E F= 0 E F= 0
Au Au
−1
−2
7+
−2
−4
6+
−3
8+ 7+
−6
−4
7+
−5 −8
Γ ∆ X K Σ X Σ K
Fig. 139. Au(100). Experimental band structure data Fig. 140. Au(110). Occupied energy bands along Σ
along ΓX (open circles) obtained from photoemission around the X-point. Experimental points from [84W2]
[89C] compared to the results of a relativistic APW compared with calculated bands from [71C]. For d-hole
calculation [71C] (solid lines). For d-hole lifetimes see lifetimes see [00C2, 01Z].
[00C2, 01Z].
0 0
Au E F (theory)
−1 −1 Λ6
−2 4 ++5 + −2
6+
−3 −3 Λ 4+5

8+
−4 6+
−4 Λ6
7+
−5 −5 Λ6
4 ++5 +
8+
−6 −6
Λ 4+5
6+
−7 −7 Λ6
−8 −8
−9 −9 6+
L Λ Γ L Λ Γ
Fig. 141. Au(111). Occupied valence band structure mental final state band (dashed in Fig. 142) was used to
along ΓL. Left panel: Solid lines represent result of derive k⊥for the experimental data points. In addition,
first-principles calculation [84E]. The data points are the calculated ground state bands have been rigidly
from [86C] and the corresponding k⊥-values were shifted down by 0.3 eV to improve visual agreement
obtained using the calculated [84E] lowest final state [86C]. For d-hole lifetimes see [00C2, 01Z].
band shown in Fig. 138. Right panel: Now the experi-
20 8−
Au Au (100)
−
6 6−
Λ 6(3)
7−
15
− hν =
6 Λ 6(1)
11.6 eV
11.0
Intensity I
Energy E [eV]
10.2
10
9.4
Λ 6(1)
8.6
7.8
5
7.0 eV
−6 −5 − 4 −3 −2 −1 0 = E F
6+
Fig. 143. Au(100). Normal-emission photoelectron

EF = 0
L Λ Γ spectra taken at different photon energies hν [78H3].
Wavevector k For photoelectrons emitted at different polar angles θ
Fig. 142. Au(111). Unoccupied energy bands above EF (hν = 10.2 eV) see also [78H3].
along ΓL [86C]. Experimental results [86C] (data points
and dashed line) are compared with calculated first
principles bands [84E]. Symmetries at L and Γ in
Au (001)-(5×20)
hν =
24 eV
23
Intensity I
22
21
20.5
20
19
18
17
16
15
14 eV
−8 −6 −4 −2 0 = EF
Fig. 144. Au(100)-(5x20). Normal-emission photoelectron spectra

recorded with s-polarized light at different photon energies hν
[94W1]. For normal-emission with 25% p-polarized light see
[94W1].
Au (100) Au (100)
(1 × 1) (5 × 20)
θ = 0° θ = 0°
45°
Intensity I
Intensity I
45°
S
50°
50°
55°
55°
60°
60°
−8 −6 −4 −2 EF = 0 −8 −6 −4 −2 EF = 0
Fig. 145. Au(100). Angle-resolved photoelectron spectra taken at different polar angles along the ΓXWK bulk mirror
plane from (left) the unreconstructed and the (5x20)-reconstructed surface (right). Photon energy hν = 21.2 eV
[79H3]. The peak labeled S is a d-like surface state [79H3].
Au (100)-(5×20) Au (100)-(1×1)
θ = 45° θ = 45°
40° 40°
35° 35°
Intensity I
Intensity I
30° 30°
25° 25°
20° 20°
15° 15°
−7 −6 −5 −4 −3 −2 −7 −6 −5 −4 −3 −2
Fig. 146. Au(100). Angle-resolved photoelectron 60 K in both cases [95M]. The intense bulk band
spectra taken at different polar angles θ along the transition observed at Ei = –6.2 eV shows an intensity-
ΓXUL bulk mirror plane. Left: (5x20) reconstructed resonance around θ = 35°, which is extremely
surface, right: (1x1) surface. Sample temperature T = temperature dependent [95M].
Au(100) Au (110)
(1 ×1)
hν =
11.6 eV
Intensity I
11.0
Intensity I
10.2
(5 × 20) 9.3
1 8.6
7.8
−2 0 = EF 2 4 6 7.0 eV
Energy E [eV] −6
−5 − 4 −3 −2 −1 0 = E F
Fig. 147. Au(100). Normal-incidence inverse Initial state energy E i [eV]
photoemission spectrum taken at an electron initial state Fig. 148. Au(110). Normal-emission photoelectron
energy Ei = 14.5 eV.The peaks labeled 1 are due to spectra taken at different photon energies hν [78H3].
image potential states. Dashed line: results for the See also [78H3] for photoelectrons excited by hν = 10.2
(100)-(1x1) surface, data points refer to the (100)- eV and emitted at different polar angles θ. For surface
(5x20) reconstructed surface [92H2]. optical properties see [02S].
Au (110)
hν = hν =
30 eV 16 eV
29 15
28 14
26 13
Intensity I
Intensity I
24 12.5
22 12.25
21.2 12
21 11.5
20 10
18 eV 8 eV
− 10 − 9 − 8 − 7 − 6 −5 − 4 −3 −2 −1 0 = E F − 10 − 9 − 8 − 7 − 6 −5 − 4 −3 −2 −1 0 = E F
Fig. 149. Au(110)-(2x1). Normal-emission photo- mirror plane [89H]. See also [89H] for band mapping
electron spectra taken at different photon energies hν. results along ΓKX. The sharp and intense feature
p-polarized light was incident at α = 60°, with the observed at 1.8 eV below EF at 12.25 eV ≤ hν ≤ 28 eV
vector potential A oriented within the ΓKLU bulk was interpreted as a surface resonance [89H].
Au (110) Au(110)-(2×1)
S2
B 2‘ S‘1
hν =
150 eV θ = 45°
40°
90
Intensity I
80 35°
30°
Intensity I
70
60 25°
S1
50 20°
40
15° S2
30 eV
10°
−12 −9 −6 −3 0 = EF B5 B6
Initial state energy E i [eV] 5° B4
B1 B2 B3
Fig. 150. Au(110)-(2x1). Normal-emission photo- 0°
electron spectra taken at different photon energies hν. EF = 0 5 10 15
p-polarized light was incident at α = 60°, with the Energy E [eV]
vector potential A oriented within the ΓKLU bulk
mirror plane [89H]. See also [89H] for band mapping Fig. 151. Au(110)-(2x1). Angle-resolved inverse photo-
results along ΓKX. emission spectra taken from the reconstructed surface at
different polar incidence angles θ along the ΓKLU bulk
mirror plane. Photon energy hν = 9.4 eV, sample at
room temperature [89D]. Several transitions into bulk
(B) and surface (S) states are identified [89D].
Au(110)-(1×1)
S2
θ = 45°
40°
35°
30°
Intensity I
25°
S1
20°
S2
15°
10° Fig. 152. Au(110)-(1x1). As Fig. 151 but with the
B5 B6
5° B3 B4 sample held at T = 1000 K to obtain the unreconstructed
B1 B2 surface. Dashed lines indicate structures only seen at the
0° reconstructed phase [89D].
EF = 0 5 10 15
Energy E [eV]
2,3 5,6
Au (111)
4
hν = 27 eV S
26
SE 25
24
D1 D2 23
D3 22
21
Intensity I
20 Fig. 153. Au(111). Normal-emission

19 photoelectron spectra taken at different
18 photon energies hν [86C].The features
17 labeled D1-D3 are assigned [86C, 86Z]
16 to surface resonances. Peak S is
15 surface state. SE labels weak structure
2 14 from secondary electron emission. The
13.5 resonance-like variation of peak
3 13 amplitudes with hν has been studied
12.5
4 12 and discussed in [86C]. See also Figs.
5,6 11 154 and 155, and see [80M] for earlier
10 work. For photoelectrons emitted at
9 different polar angles with hν = 10.2
eV see [78H3]. Ei relative to EF.
−9 −8 −7 −6 −5 − 4 −3 −2 −1 EF = 0
←
Au (111) D1 D2 D3 Fig. 154. Au(111). Normal-emission
photoelectron spectra recorded at different
photon energies hν [86C]. The features
hν = 23.3 eV labeled D1-D3 are assigned to surface
resonances [86Z]. For d-hole lifetimes see
23.0 [00C2, 01Z].
22.7 D1
22.3
22.0
Intensity I
21.7
D2
21.3
21.0
20.7 Fig. 155. Au(111). Normal-emission
20.3 D3 photoelectron spectra taken at a sample
20.0 temperature T = 150 K for different photon
19.7 energies hν (left panel). Dotted line: initial
19.3 state energies 2, 4 used to record the CIS
19.0 spectra I2, I4 in the right panel in their
18.6 dependence on sample temperature T
18.3 5 6 [96M4]. See also [78H1] for earlier work.
2,3
4 For off-normal data and corresponding one-
−8 −7 −6 −5 −4 −3 −2 step-model calculations see [96P].
Initial state energy E i [eV] ↓
Au (111)
T = 180 K
2 4 299
412
hν = 26.2 eV I2 558
663
Intensity I
25.2
24.2
23.2
16 18 20 22 24 26
22.2 Photon energy hν [eV]
Intensity I
21.2
20.2 T = 181 K
I4 280
400
19.2 569
677
Intensity I
18.2
17.2
16.2 eV
−8 −7 −6 −5 − 4 −3 −2 −1 EF = 0 16 18 20 22 24 26
A 1.0 1.0
Au (111) T = 70 K
exp.
0.8 0.8
θ = 20°
0.6 0.6
Intensity I
θ = 10°
0.4 0.4
θ = 5°
0.2 0.2
a b c
calc. A
1.0 1.0
T=0K θ = 20°
0.8 0.8
0.6
Intensity I
0.6
0.4 0.4
θ = 10°
0.2 0.2
θ = 0°
−6 −5 −4 −3 0 10 20 30 0 200 400 600

d Initial state energy E i [eV] e Emission angle θ [ ° ] f Temperature T [K]
Fig. 156. Au(111). Angle-resolved photoelectron as displayed in (b) for T = 70 K. Panel (c) shows the
spectra (a) taken at a sample temperature of T = 30 K temperature dependence of peak A at different emission
(thick line) and T = 560 K (thin line). Photon energy angles θ. Panels (d)-(f) show the same quantities as
hν = 21.2 eV, electron polar angle θ = 20° along the calculated within the framework of the fully-relativistic
ΓLUX bulk mirror plane. The intensity of the peak one-step model of photoemission [98M1].
labeled A in (a) shows a strong intensity variation with θ,
2.9 Noble metals (References) 79
2.9.5 References for 2.9
63B Burdick, G. A.: Phys. Rev. 129 (1963) 138.

63W Wyckoff, R. W. G.: Crystal Structures, John Wiley & Sons, New York, 2nd Ed., 1963.
71C Christensen, N. E., Seraphin, B. O.: Phys. Rev. B 4 (1971) 3321.
71E Eastman, D. E.: Phys. Rev. Lett. 26 (1971) 1108.
71G Gerhardt, U., Dietz, E.: Phys. Rev. Lett. 26 (1971) 1477.
72C Christensen, N. E.: Phys. Status Solidi (b) 54 (1972) 551.
73H Hüfner, S., Wertheim, G. K.: Phys. Lett. 44 A (1973) 47.
74S1 Smith, N. V.: Phys. Rev. B 9 (1974) 1365.
74S2 Smith, N. V., Wertheim, G. K., Hüfner, S., Traum, M. M.: Phys. Rev. B 10 (1974) 3197.
75J Janak, J. F., Williams, A. R., Moruzzi, V. L.: Phys. Rev. B 11 (1975) 1522.
76C Christensen, N. E.: Phys. Rev. B 13 (1976) 2698.
76D Dietz, E., Becker, H., Gerhardt, U.: Phys. Rev. Lett. 36 (1976) 1397.
76W Wehner, P. S., Stöhr, J., Apai, G., McFeely, F. R., Williams, R. S., Shirley, D. A.: Phys. Rev. B
14 (1976) 2411.
77B Battye, F., Goldmann, A., Kasper, L., Hüfner, S.: Z. Phys. B 27 (1977) 209.
77H Hermanson, J.: Solid State Commun. 22 (1977) 9.
77R Roloff, H. F., Neddermeyer, H.: Solid State Commun. 21 (1977) 561.
77W Williams, R. S., Wehner, P. S., Stöhr, J., Shirley, D. A.: Phys. Rev. Lett. 39 (1977) 302.
78C1 Citrin, P. H., Wertheim, G. K., Baer, Y.: Phys. Rev. Lett. 41 (1978) 1425.
78C2 Cardona, M., Ley, L.: Photoemission in Solids 1, Springer, Berlin, 1978.
78D1 Dietz, E., Gerhardt, U.: J. Phys. F: Metal Phys. 8 (1978) 2213.
78D2 Dietz, E., Eastman, D. E.: Phys. Rev. Lett. 41 (1978) 1674.
78E Eastman, D. E., Knapp, J. A., Himpsel, F. J.: Phys. Rev. Lett. 41 (1978) 825.
78H1 Heimann, P., Neddermeyer, H.: Solid State Commun. 26 (1978) 279.
78H2 Hansson, G. V., Flodström, S. A.: Phys. Rev. B 17 (1978) 473.
78H3 Hansson, G. V., Flodström, S. A.: Phys. Rev. B 18 (1978) 1572.
78H4 Hussain, Z., Smith, N. V.: Phys. Lett. A 66 (1978) 492.
78M Moruzzi, V. L., Janak, J. F., Williams, A. R.: Calculated electronic properties of metals:
Pergamon Press, New York, 1978.
78S Scheffler, M., Kambe, K., Forstmann, F.: Solid State Commun. 25 (1978) 93.
79C1 Courths, R., Hüfner, S., Schulz, H.: Z. Phys. B 35 (1979) 107.
79C2 Christensen, N. E.: Phys. Rev. B 20 (1979) 3205.
79D Dietz, E., Himpsel, F. J.: Solid State Commun. 30 (1979) 235.
79H1 Heimann, P., Hermanson, J., Miosga, H., Neddermeyer, H.: Phys. Rev. B 20 (1979) 3059.
79H2 Himpsel, F. J., Eberhardt, W.: Solid State Commun. 31 (1979) 747.
79H3 Heimann, P., Hermanson, J., Miosga, H., Neddermeyer, H.: Phys. Rev. Lett. 43 (1979) 1757.
79H4 Hölzl, J., Schulte, F. K.: Solid Surf. Phys., Springer Tracts Mod. Phys., Vol. 85, Springer,
Berlin, 1979.
79K1 Knapp, J. A., Himpsel, F. J., Williams, A. R., Eastman, D. E.: Phys. Rev. B 19 (1979) 2844.
79K2 Knapp, J. A., Himpsel, F. J., Eastman, D. E.: Phys. Rev. B 19 (1979) 4952.
79N Nilsson, P. O., Dahlbäck, N.: Solid State Commun. 29 (1979) 303.
79R Richardson, N. V., Sass, J. K., Lloyd, D. R., Quinn, C. M.: Surf. Sci. 80 (1979) 165.
79S Smith, N. V.: Phys. Rev. B 19 (1979) 5019.
79T Thiry, P., Chandesris, D., Lecante, J., Guillot, C., Pinchaux, R., Pétroff, Y.: Phys. Rev. Lett. 43
(1979) 82.
79W1 Wagner, C. D., Riggs, W. M., Davis, L. E., Moulder, F. J., Muilenberg, G. E.: Handbook of
XPS. Perkin-Elmer Corporation, Eden Prairie 1979.
79W2 Wehner, P. S., Williams, R. S., Kevan, S. D., Denley, D., Shirley, D. A.: Phys. Rev. B 19
(1979) 6164.
80E Eberhardt, W., Himpsel, F. J.: Phys. Rev. B 21 (1980) 5572.
80 2.9 Noble metals (References)
80M Mills, K. A., Davis, R. F., Kevan, S. D., Thornton, G., Shirley, D. A.: Phys. Rev. B 22 (1980)
581.
80P Petroff, Y., Thiry, P.: Appl. Opt. 19 (1980) 3957.
80S Smith, N. V., Benbow, R. L., Hurych, Z.: Phys. Rev. B 21 (1980) 4331.
81B Borstel, G., Neumann, M., Wöhlecke, M.: Phys. Rev. B 23 (1981) 3121.
81C1 Courths, R.: Solid State Commun. 40 (1981) 529.
81C2 Courths, R., Bachelier, V., Cord, B., Hüfner, S.: Solid State Commun. 40 (1981) 1059.
81H1 Hussain, Z., Kono, S., Petersson, L.-G., Fadley, C. S., Wagner, L. F.: Phys. Rev. B 23 (1981)
724.
81H2 Heimann, P., van der Veen, J. F., Eastman, D. E.: Solid State Commun. 38 (1981) 595.
81H3 Holloway, S., Grider, D. E., Sass, J. K.: Solid State Commun. 39 (1981) 953.
81J Jepsen, O., Gloetzel, D., Mackintosh, A. R.: Phys. Rev. B 23 (1981) 2683.
81L1 Larsson, C. G., Pendry, J. B.: J. Phys. C: Solid State Phys. 14 (1981) 3089.
81L2 Lässer, R., Smith, N. V., Benbow, R.: Phys. Rev. B 24 (1981) 1895.
81W Weaver, J. H., Krafka, C., Lynch, D. W., Koch, E. E.: Optical properties of metals, Vol. 2,
Fachinformationszentrum Physik, Karlsruhe, Germany, 1981.
82B Borstel, G., Przybylski, H., Neumann, M., Wöhlecke, M.: Phys. Rev. B 25 (1982) 2006.
82C Coleridge, P. T., Templeton, I. M.: Phys. Rev. B 25 (1982) 7818.
82D Dose, V., Reusing, G.: J. Electron Spectrosc. Relat. Phenom. 27 (1982) 261.
82G1 Grepstad, J. K., Slagsvold, B. J., Bartos, I.: J. Phys. F. Met. Phys. 12 1679.
82G2 Goldmann, A., Westphal, D., Courths, R.: Phys. Rev. B 25 (1982) 2000.
82J Jaklevic, R. C., Davis, L. C.: Phys. Rev. B 26 (1982) 5391.
82L Lindgren, S. A., Paul, J., Wallden, L.: Solid State Commun. 44 (1982) 639.
82M Martensson, H., Nilsson, P.-O., Kanski, J.: Appl. Surf. Sci. 11/12 (1982) 652.
83B1 Baalmann, A., Przybylski, M., Neumann, M., Borstel, G.: Phys. Scr. T 4 (1983) 148.
83B2 Benbow, R. L., Smith, N. V.: Phys. Rev. B 27 (1983) 3144.
83B3 Baalmann, A., Neumann, M., Neddermeyer, H., Radlik, W., Braun, W.: Ann. Israel Phys. Soc.
6 (1983) 351.
83B4 Briggs, D., Seah, M. P. (eds.), Practical Surface Analysis by Auger and X-ray Photoelectron
Spectroscopy, Wiley, New York, 1983, p. 132.
83D Dose, V., Reusing, G.: Solid State Commun. 48 (1983) 683.
83G Goldmann, A., Rodriguez, A., Feder, R.: Solid State Commun. 45 (1983) 449.
83M Martensson, H., Larsson, C. G., Nilsson, P. O.: Surf. Sci. 126 (1983) 214.
83P Przybylski, H., Baalmann, A., Borstel, G., Neumann, M.: Phys. Rev. B 27 (1983) 6669.
83S Slagvold, B. J., Grepstad, J. K., Gartland, P. O.: Phys. Scr. T4 (1983) 65.
83W Westphal, D., Goldmann, A.: Surf. Sci. 131 (1983) 92.
84A Altmann, W., Dose, V., Goldmann, A., Kolac, U., Rogozik, J.: Phys. Rev. B 29 (1984) 3015.
84C Courths, R., Hüfner, S.: Phys. Rep. 112 (1984) 53.
84E Eckardt, H., Fritsche, L., Noffke, J.: J. Phys. F: Met. Phys. 14 (1984) 97.
84M Marel, D., Sawatsky, G. A., Zeller, R., Hillebrecht, F. U., Fuggle, J. C.: Solid State Commun.
50 (1984) 47.
84R Reihl, B., Schlittler, R. R.: Phys. Rev. B 29 (1984) 2267.
84S Speier, W., Fuggle, J. C., Zeller, R., Ackermann, B., Szot, K., Hillebrecht, F. U., Campagna,
M.: Phys. Rev. B 30 (1984) 6921.
84W1 Wern, H., Leschik, G., Hau, U., Courths, R.: Solid State Commun. 50 (1984) 581.
84W2 Wöhlecke, M., Baalmann, A., Neumann, M.: Solid State Commun. 49 (1984) 217.
84Z Zimmer, H. G., Westphal, D., Kleinherbers, K. K., Goldmann, A., Richard, A.: Surf. Sci. 146
(1984) 425.
85B Baalmann, A., Neumann, M., Braun, W., Radlik, W.: Solid State Commun. 54 (1985) 583.
85G Goldmann, A., Dose, V., Borstel, G.: Phys. Rev. B 32 (1985) 1971.
85H Hulbert, S. L., Johnson, P. D., Stoffel, N. G., Smith, N. V.: Phys. Rev. B 32 (1985) 3451.
85K Krause, M. O., Sevensson, W., Carlson, T. A., Leroi, G., Ederer, D. E., Holland, D., Parr, A.
C.: J. Phys. Mol. Phys. B 18 (1985) 4069.
85M Martensson, H., Nilsson, P. O.: Surf. Sci. 152/153 (1985) 189.
85N Nelson, J. G., Kim, S., Gignac, W. J., Williams, R. S., Tobin, J. G., Robey, S. W., Shirley, D.
A.: Phys. Rev. B 32 (1985) 3465.
85P Palik, E. D., (ed.): Handbook of Optical Constants of Solids, Academic, Orlando 1985.
85R Reihl, B.: Surf. Sci. 162 (1985) 1.
85S Speier, W., Zeller, R., Fuggle, J. C.: Phys. Rev. B 32 (1985) 3597.
85W1 Wern, H., Courths, R.: Surf. Sci. 152/153 (1985) 196.
85W2 Wern, H., Courths, R.: Surf. Sci. 162 (1985) 29.
85W3 Wern, H., Courths, R., Leschik, G., Hüfner, S.: Z. Phys. B: Condens. Matter 60 (1985) 293.
85Y Yeh, J. J., Lindau, I.: At. Data Nucl. Data Tables 32 (1985) 1.
86A Altmann, W., Dose, V., Goldmann, A.: Z. Phys. B: Condens. Matter 65 (1986) 171.
86C Courths, R., Zimmer, H.-G., Goldmann, A., Saalfeld, H.: Phys. Rev. B 34 (1986) 3577.
86D Donath, M., Glöbl, M., Senftinger, B., Dose, V.: Solid State Commun. 60 (1986) 237.
86G1 Goldmann, A.: Surf. Sci. 178 (1986) 210.
86G2 Goldmann, A., Zimmer, H.-G., Courths, R., Saalfeld, H.: Solid State Commun. 57 (1986) 523.
86J Jacob, W., Dose, V., Kolac, U., Fauster, Th., Goldmann, A.: Z. Phys. B: Condens. Matter 63
(1986) 459.
86W1 White, R. C., Fadley, C. S., Sagurton, M.: Solid State Commun. 59 (1986) 633.
86W2 Woodruff, D. P., Royer, W. A., Smith, N. V.: Phys. Rev. B 34 (1986) 764.
86Z Zimmer, H.-G., Goldmann, A., Courths, R.: Surf. Sci. 176 (1986) 115.
87W White, R. C., Fadley, C. S., Sagurton, M., Roubin, P., Chandesris, D., Lecante, J., Guillot, C.,
Hussain, Z.: Phys. Rev. B 35 (1987) 1147.
88A Altmann, W., Desinger, K., Dose, V., Goldmann, A.: Solid State Commun. 65 (1988) 1411.
89C Courths, R., Wern, H., Leschik, G., Hüfner, S.: Z. Phys. B.: Condens. Matter 74 (1989) 233.
89D Drube, R., Dose, V., Derks, H., Heiland, W.: Surf. Sci. 214 (1989) L253.
89F Fauster, Th., Schneider, R., Dürr, H.: Phys. Rev. B 40 (1989) 7981.
89H Hansen, J. C., Benson, J. A., Wagner, M. K., Tobin, J. G.: Solid State Commun. 69 (1989)
1197.
89K1 Kim, B., Hong, S., Lin, R., Lynch, D. W.: Phys. Rev. B 40 (1989) 10238.
89K2 Krummacher, S., Sen, N., Gudat, W., Johnson, R., Grey, F., Ghijsen, J.: Z. Phys. B: Condens.
Matter 75 (1989) 235.
89K3 Kwawer, G. N., Miller, T. J., Mason, M. G., Tan, Y., Brown, F. C., Ma, Y.: Phys. Rev. B 39
(1989) 1417.
89S Schneider, C. M., Garbe, J., Bethke, K., Kirschner, J.: Phys. Rev. B 39 (1989) 1031.
89T Tamura, E., Feder, R., Vogt, B., Schmiedeskamp, B., Heinzmann, U.: Z. Phys. B: Condens.
Matter 77 (1989) 129.
89W1 Wu, S. C., Sokolov, J., Lok, C. K. C., Quinn, J., Li, Y. S., Tian, D., Jona, F.: Phys. Rev. B 39
(1989) 12891.
89W2 Wu, S. C., Lok, C. K. C., Sokolov, J., Quinn, J., Li, Y. S., Tian, D., Jona, F.: J. Phys. Condens.
Matter 1 (1989) 4795.
89W3 Wu, S. C., Li, H., Sokolov, J., Quinn, J., Li, Y. S., Jona, F.: J. Phys.: Condens. Matter 1 (1989)
7471.
90E Edamoto, K., Miyazaki, E., Skimokoshi, K., Kato, H.: Phys. Scripta 41 (1990) 91.
90F Fuster, G., Tyler, J. M., Brener, N. E., Callaway, J., Bagayoko, D.: Phys. Rev. B 42 (1990)
7322.
90L Lange, C., Mandel, T., Laubschat, C., Kaindl, G.: J. Electron Spectrosc. Relat. Phenom. 52
(1990) 49.
90S Schneider, R., Dürr, H., Fauster, Th., Dose, V.: Phys. Rev. B 42 (1990) 1638.
91G Goldmann, A., Altmann, W., Dose, V.: Solid State Commun. 79 (1991) 511.
91Q Quinten, M., Sander, I., Steiner, P., Kreibig, U., Fauth, K., Schmid, G.: Z. Phys. D: At. Mol.
Clusters 20 (1991) 377.
92F Fuggle, J. C., Inglesfield, J. E., (eds.): Unoccupied Electronic States, Vol. 69, Topics Appl.
Phys., Springer, Berlin-Heidelberg, 1992.
92H1 Hwu, Y., Lozzi, L., La Rosa, S., Onellion, M., Almeras, P., Gozzo, F., Lévy, F., Berger, H.,
Margaritondo, G.: Phys. Rev. B 45 (1992) 5438.
82 2.9 Noble metals (References)
92H2 Himpsel, F. J., Ortega, J. E.: Phys. Rev. B 46 (1992) 9719.

92S1 Schneider, R., Dose, V.: Chapter 9 in [92F], p. 277 ff.
92S2 Smith, N. V.: Comments Condens. Matter. Phys. 15 (1992) 263.
93G Goldmann, A., Matzdorf, R.: Progr. Surf. Sci. 42 (1993) 331.
93H Halilov, S., Gollisch, H., Tamura, E., Feder, R.: J. Phys.: Condens. Matter 5 (1993) 4711.
93L1 Lau, M., Löbus, S., Courths, R., Halilov, S., Gollisch, H., Feder, R.: Ann. Phys. 2 (1993) 450.
93L2 Löbus, S., Lau, M., Courths, R., Halilov, S.: Surf. Sci. 287/288 (1993) 568.
93M1 Matzdorf, R., Meister, G., Goldmann, A.: Surf. Sci. 286 (1993) 56.
93M2 Matzdorf, R., Meister, G., Goldmann, A.: Surf. Sci. 296 (1993) 241.
93S1 Smith, N. V., Thiry, P., Pétroff, Y.: Phys. Rev. B 47 (1993) 15476.
93S2 Starnberg, H. I., Bauer, H. E., Nilsson, P. O.: Phys. Rev. B 48 (1993) 621.
94A Aebi, P., Osterwalder, J., Fasel, R., Naumovic, D., Schlapbach, L.: Surf. Sci. 307-309 (1994)
917.
94M1 Matzdorf, R., Goldmann, A.: Solid State Commun. 91 (1994) 163.
94M2 Matzdorf, R., Paniago, R., Meister, G., Goldmann, A.: Solid State Commun. 92 (1994) 839.
94W1 Wu, S. C., Li, H., Quinn, J., Tian, D., Li, Y. S., Begley, A. M., Kim, S. K., Jona, F., Marcus, P.
M.: Phys. Rev. B 49 (1994) 8353.
95H Hüfner, S.: Photoelectron Spectroscopy - Principles and Applications, Vol. 82 Springer Ser.
Solid-State Sci., Springer, Berlin-Heidelberg, 1995.
95K Krasovskii, E. E., Schattke, W.: Solid State Commun. 93 (1995) 775.
95M Matzdorf, R., Paniago, R., Meister, G., Goldmann, A., Courths, R.: Surf. Sci. Lett. 343 (1995)
L1182.
95Q Qu, Z., Goonewardene, A., Subramanian, K., Karunamuni, J., Mainkar, N., Ye, L., Stockbauer,
R. L., Kurtz, R. L.: Surf. Sci. 324 (1995) 133.
96L Löbus, S., Courths, R., Halilov, S., Gollisch, H., Feder, R.: Surf. Rev. Lett. 3 (1996) 1749.
96M1 Matzdorf, R., Meister, G., Goldmann, A.: Phys. Rev. B 54 (1996) 14807.
96M2 Matzdorf, R., Goldmann, A.: Surf. Sci. 359 (1996) 77.
96M3 Miller, T., McMahon, W. E., Chiang, T.-C.: Phys. Rev. Lett. 77 (1996) 1167.
96M4 Matzdorf, R., Paniago, R., Meister, G., Goldmann, A., Zubrägel, Ch., Braun, J., Borstel, G.:
Surf. Sci. 352-354 (1996) 670.
96O Osterwalder, J., Greber, T., Aebi, P., Fasel, R., Schlapbach, L.: Phys. Rev. B 53 (1996) 10209.
96P Paniago, R., Matzdorf, R., Meister, G., Goldmann, A., Braun, J., Borstel, G.: Surf. Sci. 347
(1996) 46.
96S Strocov, V. N., Starnberg, H. I., Nilsson, P. O.: J. Phys.: Condens. Matter 8 (1996) 7539.
97H Hansen, E. D., Miller, T., Chiang, T.-C.: Phys. Rev. B 55 (1997) 1871.
97M Miller, T., Hansen, E. D., McMahon, W. E., Chiang, T.-C.: Surf. Sci. 376 (1997) 32.
97O Ogawa, S., Nagano, H., Petek, H.: Phys. Rev. B 55 (1997) 10869.
97P1 Pawlik, S., Bauer, M., Aeschlimann, M.: Surf. Sci. 377-379 (1997) 206.
97P2 Petek, H., Ogawa, S.: Progr. Surf. Sci. 56 (1997) 239.
97W Wolf, M.: Surf. Sci. 377-379 (1997) 343.
98A Aebi, P., Fasel, R., Naumovic, D., Hayoz, J., Pillo, Th., Bovet, M., Agostino, R. G., Patthey,
L., Schlapbach, L., Gil, F. P., Berger, H., Kreutz, T. J., Osterwalder, J.: Surf. Sci. 402-404
(1998) 614.
98F Fluchtmann, M., Bei der Kellen, S., Braun, J., Borstel, G.: Surf. Sci. 402-404 (1998) 663.
98G Gerlach, A., Matzdorf, R., Goldmann, A.: Phys. Rev. B 58 (1998) 10969.
98H Hansen, E. D., Miller, T., Chiang, T.-C.: Phys. Rev. Lett. 80 (1998) 1766.
98K Knoesel, E., Hotzel, A., Wolf, M.: Phys. Rev. B 57 (1998) 12812.
98M1 Matzdorf, R.: Surf. Sci. Rep. 30 (1998) 153.
98M2 Matzdorf, R., Goldmann, A.: Surf. Sci. 400 (1998) 329.
98M3 Matzdorf, R., Gerlach, A., Hennig, R., Lauff, G., Goldmann, A.: J. Electron Spectr. Relat.
Phenom. 94 (1998) 279.
98P Pawlik, S., Burgermeister, R., Bauer, M., Aeschlimann, M.: Surf. Sci. 402-404 (1998) 556.
99C Courths, R., Löbus, S., Halilov, S., Scheunemann, T., Gollisch, H., Feder, R.: Phys Rev. B 60
(1999) 8055.
99H Hüfner, S., Claessen, R., Reinert, F., Straub, Th., Strocov, V. N., Steiner, P.: J. Electron
Spectrosc. Relat. Phenom. 100 (1999) 191.
99M Matzdorf, R., Gerlach, A., Goldmann, A., Fluchtmann, M., Braun, J.: Surf. Sci. 421 (1999)
167.
99P1 Paggel, J. J., Miller, T., Chiang, T.-C.: Phys. Rev. Lett. 83 (1999) 1415.
99P2 Petek, H., Ogawa, S.: Phys. Rev. Lett. 83 (1999) 832.
00C1 Campillo, I., Pitarke, J. M., Rubio, A., Echenique, P. M.: Phys. Rev. B 62 (2000) 1500.
00C2 Campillo, I., Rubio, A., Pitarke, J. M., Goldmann, A., Echenique, P. M.: Phys. Rev. Lett. 85
(2000) 3241.
00C3 Chiang, T.-C.: Chem. Phys. 251 (2000) 133.
00E Echenique, P. M., Pitarke, J. M., Chulkov, E. V., Rubio, A.: Chem. Phys. 251 (2000) 1.
00K Kliewer, J., Berndt, R., Chulkov, E. V., Silkin, V. M., Echenique, P. M., Crampin, S.: Science
288 (2000) 1399.
00L Luh, D. A., Paggel, J. J., Miller, T., Chiang, T.-C.: Phys. Rev. Lett. 84 (2000) 3410.
00M Michalke, T., Gerlach, A., Berge, K., Matzdorf, R., Goldmann, A.: Phys. Rev. B 62 (2000)
10544.
00N Nicolay, G., Reinert, F., Schmidt, S., Ehm, D., Steiner, P., Hüfner, S.: Phys. Rev. B 62 (2000)
1631.
00P1 Petek, H., Nagano, H., Weida, M. J., Ogawa, S.: Chem. Phys. 251 (2000) 71.
00P2 Paggel, J. J., Miller, T., Chiang, T.-C.: Phys. Rev. B 61 (2000) 1804.
01G Gerlach, A., Berge, K., Goldmann, A., Campillo, I., Rubio, A., Pitarke, J. M., Echenique, P.
M.: Phys. Rev. B 64 (2001) 085423.
01P Pforte, F., Michalke, T., Gerlach, A., Goldmann, A., Matzdorf, R.: Phys. Rev. B 63 (2001)
115405.
01S1 Strocov, V. N., Claessen, R., Nicolay, G., Hüfner, S., Kimura, A., Harasawa, A., Shin, S.,
Kakizaki, A., Starnberg, H. I., Nilsson, P. O., Blaha, P.: Phys. Rev. B 63 (2001) 205108.
01S2 Stahrenberg, K., Herrmann, Th., Wilmers, K., Esser, N., Richter, W.: Phys. Rev. B 64 (2001)
115111.
195122.
02B Berge, K., Gerlach, A., Meister, G., Goldmann, A., Braun, J.: Surf. Sci. 498 (2002) 1.
02G Gerlach, A., Berge, K., Michalke, T., Goldmann, A., Müller, R., Janowitz, C.: Surf. Sci. 497
(2002) 311.
02M Marini, A., Onida, G., Del Sole, R.: Phys. Rev. Lett. 88 (2002) 016403.
02S Stahrenberg, K., Herrmann, Th., Esser, N., Richter, W., Hoffmann, S. V., Hofmann, Ph.: Phys.
Rev. B 65 (2002) 035407.
02T Tang, Z., Hasegawa, M., Nagai, Y., Saito, M.: Phys. Rev. B 65 (2002) 195108.
115116.
84 2.10 Noble metal halides (Introduction) [Ref. p. 156
2.10 Noble metal halides
2.10.1 Introduction
This chapter collects data on CuCl, CuBr, CuI, AgF, AgCl, AgBr and AgI. These I-VII compounds
exhibit Phillips ionicities fi just at the border line between tetrahedral and octahedral coordination. Values
of fi for the Cu- and Ag-halides are as follows: CuF (fi =0.766), CuCl (0.746), CuBr (0.735), CuI (0.692),
AgF (0.894), AgCl (0.856), AgBr (0.850) and AgI (0.770). Whereas the Cu-halides and AgI still form the
zincblende or the wurtzite lattice at normal pressure and room temperature, in AgF, AgCl and AgBr the
ionicity is already so large that the rocksalt structure is favoured energetically. Thus the Cu- and Ag-
halides are situated in the region between tetrahedral and octahedral coordination, which in turn leads to
the existence of a variety of high-pressure phases, polymorphs and a rather complex phase diagram. For
details we refer to Landolt-Börnstein volumes on “Semiconductors”, i.e. Vol. III/41B or previous
volumes III/17b and III/22a, and to references [77G, 81V, 86B, 98H].
Since CuF is chemically very unstable, no photoemission experiments were performed so far. In
contrast CuCl, CuBr and CuI have received very much attention, both from experiment and theory. This
interest results from the fact that their valence bands originate from the filled d10-shell of the metal+ -ions
and the s2p6 rare gas configuration of the halogen-ions. This is in contrast to the III-V and many other I-
VII compounds whose valence bands also originate from a s2p6 configuration, but with the metal d-levels
energetically well below the valence region. In the Cu-halides the spatial extent of the d-levels is large,
their energies are close to those of the halogen p-levels, and a strong p-d hybridization results. Thus the
zincblende lattice of the Cu-halides is built up by directed sp3 - sd3 bonds. In consequence these
compounds show several physical properties significantly altered if compared to the other members of the
group IV, III-V and II-VI isomorphic series. For example it was observed already very early [63C] that in
CuCl the spin-orbit splitting of the edge exciton is reversed from that of "normal" zincblende
semiconductors. The bulk moduli are very much smaller than those of their isostructural neighbours
[72H]. Also, the small magnitude [81V, 83B, 84C] of the deformation potentials of gaps and valence-
state splittings related to hydrostatic and uniaxial strains can be attributed to strong d-p hybridization
[86B]. The d10-admixture increases the number of valence electrons per formula unit from 8 (sp3-bonds)
to 18, and this fact considerably complicates the task of calculating the energy-band structure of these
materials. In consequence, a variety of techniques was used, both in nonrelativistic and relativistic
versions, to figure out to which extent the calculated energy bands and the corresponding densities of
states may explain the experimental data. Many of these theoretical results are reproduced in the present
chapter.
The silver halides are of important technical interest as photographic material. The promotion of
electrons from the valence to the conduction bands by light absorption plays a major role in the
photographic process [88H, 93K]. Also they are of importance as solid electrolytes [82M, 87E], with α-
AgI having an ionic conductivity similar to molten salts, and as liquid semiconductors [90E]. Moreover,
the growth of bulk silver halide adlayers as well as halide-modified Ag surfaces are of relevance for
catalytic surface properties, interfacial electrochemistry, sensors and the development of thin-film solid
lubricants. Besides this technical importance the nearly energetic degeneracy of the metal d orbitals with
those of the halogen attracts basic interest. The strong p-d hybridization causes AgF, AgCl and AgBr to
have indirect band gaps, in contrast to their isoelectronic neighbours CuCl and CuBr. In consequence
there was and still is considerable effort to understand the electronic properties of both the Cu- and Ag-
halides and this ongoing interest explains the large amount of data available for these compounds.
Ref. p. 156] 2.10 Noble metal halides (Introduction) 85
As a result of the p-d orbital mixing the photoelectron spectra are composites of both the halogen and
metal partial densities of states. Their relative intensities will therefore vary with photon energy according
to the corresponding photoionization cross sections, and these variations may be drastic. For example
going from hν = 21.2 eV (HeI) to hν = 40.8 eV (HeII) decreases the metal cross sections by a factor of
about 1.3 (Cu) and 1.04 (Ag), respectively [74G1]. In contrast the excitation probabilities for the halogen
atoms go down by factors of about 15.2, 10.9 and 30.3 for Cl, Br and I [74G1]. Using either experimental
or theoretical cross-section ratios (at appropriate photon energies) as an input allows approximate partial
p and d densities to be deduced from the experimental photelectron energy distribution curves. This
procedure was applied in several studies, and for further details of the analysis, various sources of
experimental or calculated cross-section data and a discussion on possible p-d interference effects, we
refer to the literature [72K1, 72K2, 73K, 74E2, 74G1, 74K1, 74K2, 74T, 75T, 77G, 78P, 79L, 80B, 80M,
86S, 90M, 91S, 93M1].
Most experimental data reported in the following are taken from thin films, typically at a thickness of
only a few hundred Å. These films, deposited either epitaxially or as polycrystalline material, generally
have enough photoconductivity to avoid sample charging. Special care is necessary since during exposure
to ultraviolet photons and soft X-rays at room temperature severe damage effects may be observed, in
particular if high-intensity synchrotron radiation is used [93M2]. Photolysis is, however, almost
completely quenched at liquid nitrogen temperature [78C, 89K, 91W, 93M2]. At these low temperatures
interstitial Cu+ and Ag+ migration is significantly slowed and this fact inhibits latent-image formation by
metal atom clustering. Taking photoelectron spectra at low temperatures has the additional advantage that
linewidths are significantly narrowed [76B1, 76B2, 76L].
Landolt-Börnstein Vol. III/41B as well as previous volumes III/17b and III/22a summarize very
extensively data on the following quantities: gap energies, corresponding pressure coefficients and
deformation potentials, exciton parameters like energies and splittings and masses, g-factors, biexcitons,
lattice properties, phonon frequencies and linear as well as non-linear optical constants. These data are
therefore not collected systematically in this chapter. For most recent data on nanocrystals we refer to
[99E, 99O, 99Z, 00G, 00V], see also Landolt-Börnstein Vol. III/34C1, Chap. 6 (publ: in 2001).
86 2.10 Noble metal halides (CuCl) [Ref. p. 156
2.10.2 CuCl (Cuprous chloride)
At normal conditions CuCl crystallizes in the zincblende structure (γ-CuCl):

Lattice fcc, a = 5.4057 Å [63W],
space group Td2 - F 4 3m,
Brillouin zones see section 1.3 of this volume.
Work-function (γ-CuCl):
φ (polycrystalline) = 6.8(4) eV [74G1], 7.0(2) eV [79P], 6.9(2) eV [83G]
φ (100) = 7.0(2) eV [83G]
φ (111) = 6.8(2) eV [83G]
Direct band gap at Γ with Eg = 3.395 eV at T = 4K as best value extrapolated from various optical results
[77G]. At room temperature Eg = 3.17eV (at zero pressure) has been derived from experiments studying
the absorption edge under hydrostatic pressure [81V]. Bulk plasmon energy !ωp = 20.9(5)eV [74G1]. For
excitonic and phononic properties of CuCl nanocrystals see [99E, 99O, 99Z] or Landolt-Börnstein, Vol.
III/34C1, Chap. 6.
For the phase diagram and structural details of high-temperature / high pressure phases see Landolt-
Börnstein Vols. III/41B, III/17b and [81V, 86B].
Table 1. γ-CuCl. Copper core-level binding energies

in eV relative to the top of the valence band [74G1].
Level n=2 n=3
ns1/2 1095.3(2) 121.2
np1/2 950.8 76.5(2)
np3/2 931.0 74.0(2)
Errors ±0.1eV unless otherwise stated. If referred to the vacuum level the Cu-ion core levels show a
chemical shift of 1.1(5)eV and are more tightly bound in CuCl than in metallic copper [74G1].
Table 2. γ-CuCl. Occupied valence bands. Critical point energies determined by

different experiments. Experimental errors are ± 0.1eV if not explicitly given in
parentheses. Energy values are given in eV with respect to the top of the valence band.
Symmetries are indicated in double (single) group notation.
Symmetry UPS ARUPS ARUPS Reflectivity
Points [77G] [80W] [83G] [83L]
Γ7,8 (Γ15) 0 0 0 0
Γ8 (Γ12)b) –1.9 –2.0 –1.9 –1.5
Γ7,8 (Γ15) –3.5 –5.0 –4.9 –3.4
Γ6 (Γ1) –15.8(2)a) – –15.8(2)a) –15.7
X6,7 (X5) –1.3 –1.05 –1.0 –
X6 (X3) –1.5 –1.5 –1.5 –
X6,7 (X5) –5.1 – –4.9 –3.4
X6 (X3) –6.9 –6.15 –6.1 –4.9
X7 (X3) –15.8(2)a) – –15.8(2)a) –15.7
cont.
Ref. p. 156] 2.10 Noble metal halides (CuCl) 87
Table 2 (cont.)
Symmetry UPS ARUPS ARUPS Reflectivity

Points [77G] [80W] [83G] [83L]
L4,5,6 (L3) –1.0 –0.55 –0.6 –0.9
L4,5,6 (L1) –1.5 –1.35 –1.9 –3.4
L6 (L3) –4.6 – –4.9 –4.9
L4,5,6 (L1) –6.8 –6.3 –6.1 –
L6 (L1) –15.8(2)a) – –15.8(2)a) –15.7
a) Data taken from [74G1].
b) The Γ point has been located at –1.79 eV by two-photon absorption at T = 4.3 K [82F1].
12
Table 3. γ-CuCl. Unoccupied bands of the bulk. Experimental energies of symmetry points are given in
eV with respect to the top of the valence band. Symmetries are given in single group notation.
Symmetry Γ15 X1 X5 X3 Γ15 L1 L3 L1
ARUPS 9.6(2) 7.8(2) 9.6(2) 12.1(2) – 8.1(2) 9.6(2) 11.4(3)

[83G]
Reflectivity 9.7 7.2 – 12.6 17.5 8.7 – 11.4
[83L]
Others – 7.3 a) – 12.3 b) 17.5 a) 8.5 a) – 11.7 a)

17.7 b) 8.6 b)
a) Deduced from Cl(2p) core-level absorption [71S].

b) Deduced from Cl(1s) core-level absorption [73S].
Table 4. γ-CuCl. Calculated critical point energies at Γ according to different authors. All data given in
eV relative to the top of the valence band. Symmetries are given in double (single) group notation.
Symmetry [67S] [73C] [79D] [79K1] [79K2] [79Z] [80O] [83L]

Point
Γ7,8 (Γ15) +10.9 +9.4 +10.1 +10.13 – +9.6 – +9.7

Γ6 (Γ1) +3.4 +3.4 +3.07 +4.32 +3.1 +2 +3.57 +3.4
Γ7,8 (Γ15) 0 0 0 0 0 0 0 0
Γ8 (Γ12) –0.6 –1.41 –1.0 –3.4 –1.5 –1.33 –1.14 –1.47
Γ7,8 (Γ15) –2.7 –4.42 –3.13 –7.46 –3.8 –4.9 –4.3 –3.4
Γ6 (Γ1) –18 –16 –15.6 –25.7 –15.7 –16.8 – –15.7
The occupied Γ12 state has been calculated at –1.80eV using a quasimolecular approach [83E].
The fraction of p-like density of states at the γ-phase valence band edge has been determined in many
experimental and theoretical studies. All experimental data range between 21 and 25% [77G], while
calculated values scatter between 21 and 40% [83L]. The percentage of different symmetry types (s,p,d)
integrated within each band has been calculated in [83L].
Figures for 2.10.2
2
10
8
6
4 Cl
2
10
8
6
4
2
1
8
6
4
2p
2
2s
–1
10
8
6
4
3p
2
–2 3s
10 8
Fig. 1. CuCl. Atomic subshell
6 photoionization cross sections of
4
chlorine for photon energies from
2 0 to 1500 eV [85Y]. For atomic
–3 copper see Fig. 1 in section 2.9.
10
0 200 400 600 800 1000 1200 1400 1600
3.0
CuCl
2.5
2.0
1.5
1.0
Fig. 2. γ-CuCl. XPS valence band spectrum taken from
0.5
a polycrystalline sample with unmonochromatized
EF MgKα radiation at hv = 1253.6 eV [73K]. See also
[74G1]. For the results of a deconvolution which
0 corrects for experimental broadening see [73K].
–11 –9 –7 –5 –3 –1 0 1
Initial state energy Ei [eV]
0.6 2.5
hν = 48.4 eV CuCl
CuCl hν = 76 eV
0.4 2.0
0.2
(× 6) 1.5
0
6
hν = 40.8 eV 1.0
4 EF
0.5
2 (× 7)
0
0 –12 – 10 –8 –6 –4 –2 0 2
1.8 Initial state energy Ei [eV]
hν = 26.9 eV 7
hν = 61 eV
1.2 6
0.6 5
4
0
6
hν = 21.2 eV
3
4
2
2 1
EF
0 0
18 –12 – 10 –8 –6 –4 –2 0 2
hν = 16.8 eV Initial state energy Ei [eV]
3.5
12 hν = 40 eV
3.0
6
EVBM 2.5
0
–8 –6 –4 –2 0 2.0
1.5
Fig. 3. γ-CuCl. Photoelectron spectra taken for different
photon energies from polycrystalline films. Dashed lines
indicate estimated secondary electron background 1.0
[74G1].
→ 0.5
Fig. 4. γ-CuCl. Photoelectron spectra taken at different EF
photon energies hv from polycrystalline films [74I]. 0
–12 – 10 –8 –6 –4 –2 0 2
15.0
CuCl CuCl
12.5
Absorption coefficient α [10 cm ]

–1
10.0
5
7.5
5.0
2.5
2 4 6 8 10 12 14 16 18 20 22 0 5 10 15 20 25 30
Final state energy Ef [eV] Photon energy hν [eV]
Fig. 5. γ-CuCl. Bremsstrahlung-isochromat spectrum Fig. 6. γ-CuCl. Absorption spectrum taken from a
(BIS) taken at hv = 1486.6 eV, sample holder kept at polycrystalline sample at liquid nitrogen temperature
liquid nitrogen temperature [94L]. The energy scale was [72I].
calibrated by the author of this chapter using Fig. 1 in
[90H]. It may be accurate to ±1 eV and refers to energy
zero at valence band maximum.
40
CuCl
8.47
35 10.30
9.70
30
9.30 14.65
25 7.35 12.07
Reflectivity R [%]
6.80 13.90
11.17 13.10
20 5.90
15
10 Fig. 7. γ-CuCl. Reflection

spectrum taken at a sample
temperature of T = 6 K [83L]. All
5 energies given in eV. For data
taken at other temperatures see
0 [80G1, 80G2] and [77L].
5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0
CuCl
a
Absorption
Fig. 8. γ-CuCl. X-ray absorption spectra measured at

(a) the CuK edge and (b) the ClK edge [90H]. The
energy is referred to the valence band maximum.
0 10 20 30 40 50
Energy E [eV]
0
CuCl EVBM 15
3
–1 5 1 5
1 3 12
–2 1
–3
–4
5 3 5 Fig. 10. γ-CuCl. Semirelativistic

–5 15
band structure obtained from a
self-consistent local-density poten-
tial with the LMTO-ASA method
–6 [81V, 82G]. For the effects of a
3 1 3
2% reduced lattice constant see
[81V]. Symmetries given in single
–7 group notation.
Γ X W L Γ K X
Wavevector k
8
CuCl
7
7
6
6
6
5
4
6 6
3
2
Energy E [eV]
7 EVBM 7 6
0
8 8 4,5
7
6
–1 4,5
8 7 8 6
–2
–3
–4
8 6 8 6 Fig. 9. γ-CuCl. Energy bands
7 7 7 4,5 calculated using the relativistic
–5 KKR method and neutral atomic
6 6 potentials [80O]. Symmetries given
–6 in double group notation.
Γ X Γ L
Wavevector k
0
EVBM Γ15 (d)
CuCl
–1 Γ12 (d)
–2
–3
–4
Γ15 (p)
–5
–6 Fig. 11. γ-CuCl. Energy position of critical points as

obtained experimentally (broken lines [82W]) and from
–7 X3 (p) various calculations: + [67S], o [79D], x [79K1], ❏
[79K2], ∆ [80H], ▲ [73C], ∇ [80O], ● [79Z], ■
–8 [81V, 82G], ◊ [79V].
EVBM 15 (7)
0
CuCl (8)
– 0.5
–1.0
–1.5
12
(8)
–2.0
–2.5
–3.0
–3.5
– 4.0
– 4.5 15 (8)
(7)
– 5.0
– 5.5
– 6.0
L Γ K X Γ
Wavevector k
Fig. 12. γ-CuCl. Band structure calculated with the self-consistent relativistic
LMTO-ASA method with "empty spheres" [82B]. Energy with respect to
VBM. Symmetries given in (double) and single group notation.
13
3 6,7 2
12 4,5 1
11
CuCl 6
10 1,2
7,8
9
6 1
8
7 6
6
4 7
5 1
6
4 6
3
Energy E [eV]
2
1
EVBM 7,8
0
2 6,6,7 4,5 6,6 2
–1 1 1
42 6,7 8 4,5 1 2,1
–2 3 6
–3 4,5 2
4 6,7 7,8 6 1
–4 1
2
6 1
–5 6
–6 Fig. 13. γ-CuCl. Parametrized
band structure obtained by a
–13 Slater-Koster fit to high-symmetry
–14 points (Γ,X,L) derived experimen-
tally from reflection spectra [83L].
–15 7 6 6 1 Symmetries given in double group
3
–16 notation.
W X Γ L K Γ
Wavevector k
CuCl
DOS
Fig. 14. γ-CuCl. Total density of

valence and conduction states
calculated from the parametrized
band structure shown in Fig. 13.
Energy referenced to the valence
band maximum [83L].
–16 –15 –5 –3 –1 0 1 3 5 7 9 11 13
Energy E – EVBM [eV]
7 CuCl
+
6
5
6+
2
Energy E [eV]
1 6
+
+
4
0
+ +
6 ,7 6+
+ +
8 ,7 7+ 6+
–1 8
+ 6+ 4
+
– +
8 7
6–
–2 7
–
–
6
4+
–3 6
+
–
6
–4
+
6
–5
Γ ∆ X L Λ Γ Σ K X
Wavevector k
Fig. 15. CuCl (rocksalt phase). Relativistic band CuCl in the rocksalt phase obtained from a self-
structure calculated from a standard muffin-tin potential consistent local-density-potential with the LMTO-ASA
with the KKR method [81V]. This phase is observed method. For a scalar-relativistic LMTO self-consistent
only at high pressures above about 9 GPa [81V]. These band structure of the high pressure tetragonal phase of
authors also present a semirelativistic band structure of CuCl see [86B].
16 B
CuCl CuCl(100) clean
12 3(4) S1
1(5)
13.1
15(3)
3(4) 5(3)
8 1(4) 1(3) C
Evac
11.2
12.1
1(3) 3(3)
14.6
4
16.1
8.5
A
Energy E [eV]
1(2)
9.3
17.5
7.4
5.9
EVBM
8.2
6.8
15(2)
0 3(3) 5(2) EVBM
3(2) S2
10.3
3(2)
12(1) 1(2)
9.7
–4 15(1)
3(1) 5(1)
20.7
1(2) 3(1)
EF
–8
–12 –8 –7 –6 –5 – 4 –3 –2 –1 0 1
a Initial state energy Ei [eV]
1(1) 1(1) 1(1)
–16 B 104 L O2
L Γ X C
Wavevector k
Fig. 16. γ-CuCl. Empirical band structure model based

on experimental critical point energies obtained from
photoemission spectra [83G]. The vertical arrows give A
the interpretation [83G] of structures observed in
reflection spectra [80G1, 80G2] in terms of direct
transitions between critical points at Γ, L and X [83G].
See also [80G2]. – Energy referenced to VBM.
S1 EVBM
S2
For Fig. 17 see next page EF
–8 –7 –6 –5 – 4 –3 –2 –1 0 1
b Initial state energy Ei [eV]
Fig. 18. γ-CuCl (100). Normal-emission photoelectrons

recorded at hν = 21.2 eV from a clean (a) sample and a
surface (b) contaminated by exposure to 104L O2 at
room temperature. Both spectra taken at T = 130 K
[80W]. The difference curve a-b is shown shaded in (a)
and identifies peaks S2 and S1 as surface state and
surface resonance, resp. [80W]. Labels A, B, C identify
bulk band emission. See also [98T] for a surface state at
E ≈ 9 eV below valence band maximum.
B
CuCl(100)
S1
F1
C
F2
F3
A
hν =
21.2 eV
S2
a
a
∆hν hν =
21.2 eV
b ∆hν
∆hν
hν = 16.8 eV
VBM + hν
c
4 6 8 10 12 14 16 18 20 22 24
Final state energy Ef [eV]
Fig. 17. γ-CuCl (100). Normal-emission photoelectron spectra observed

after excitation by photons with hν = 21.2 eV (a,b) and hν = 16.8 eV (c),
and plotted versus the final state energy [83G]. The low-energy cut-off is
located at about 6.9 eV. Structures labeled F1-F3 are due to SEE from final
state bulk critical points. The other labels refer to surface state (S2), surface
resonance (S1) and bulk band (A, B, C) photoemission, respectively. All
data taken at T = 130 K. Spectra (a,b) differ slightly due to better surface
quality of (a) as judged by a more brillant LEED pattern and additional SEE
fine structures a, b [83G]. Energy referenced to VBM.
CuCl(100) X3 hν = 40.8 eV CuCl(100)

Γ12
X5
S2
X5 S1
X3 EVBM θ = 60°
d
hν = 21.2 eV
50°
B
S1
C 40°
A X5
S2 30°
c EVBM
20°
B hν = 16.9 eV
10°
0°
A EVBM
C
X5
S2 S1 E –9 –8 –7 – 6 –5 – 4 –3 –2 –1 0 1
VBM Initial state energy Ei [eV]
b
Fig. 21. γ-CuCl (100). Photoelectron spectra taken at hν
A hν = 11.8 eV = 21.2 eV for different polar angles θ in the ΓXWK
X5 plane [82W]. For similar data at hν = 23 eV see [98T].
S1 See also [80W].
S2
sec EVBM
a
–8 –7 –6 –5 – 4 –3 –2 –1 0 1
Fig. 19. γ-CuCl (100). Normal-emission photoelectron

spectra taken at different photon energies with the
sample at T = 130 K [82W]. "Sec" indicates the
secondary electron cut-off. Energy referred to VBM =
0. Labels Γ and X indicate position of critical point
energies of the valence band structure. The other labels
identify peaks resulting from surface (S1, S2) and bulk
(A, B, C) emission, respectively.
CuCl(100)
hν = 12.7 eV
hν = 26.3 eV
14.4 eV
17.1 eV
30.4 eV
19.5 eV
34.5 eV
40.7 eV
EF EF
–6 –5 –4 –3 –2 –1 0 –10 – 9 – 8 – 7 – 6 –5 – 4 –3 –2 –1 0 1 2
Initial state energy Ei [eV] Initial state energy Ei [eV]
Fig. 20. γ-CuCl (100). Normal-emission photoelectron spectra taken at different photon energies with the sample at
room temperature [98T]. The energy references to EF = 0.
CuCl(111) A CuCl(111)
hν = 40.8 eV
θ = 65°
EVBM
d
50°
hν = 21.2 eV B
C
40°
A
30°
EVBM
c
hν = 16.9 eV L3
20°
10°
L3
L1
sec 5°
EVBM
b
hν = 11.8 eV Γ12 0°
EVBM
–9 –8 –7 – 6 –5 – 4 –3 –2 –1 0 1
sec Initial state energy Ei [eV]
EVBM
a Fig. 23. γ-CuCl (111). Angle-dependent photoelectron
–9 –8 –7 – 6 –5 – 4 –3 –2 –1 0 1 spectra recorded at hν = 21.2 eV for different polar
Initial state energy Ei [eV] angles θ along ΓXWK. Sample temperature T = 130 K
[82W].
Fig. 22. γ-CuCl (111). Normal-emission photoelectron
spectra taken at different photon energies with the
sample at T = 130 K [82W]. "Sec" labels features due to
the low-energy secondary electron cut-off. Labels Γ, L
indicate critical point energies of the valence band
structure; A, B, C identify emission from bulk bands.
Ref. p. 156] 2.10 Noble metal halides (CuBr) 101
2.10.3 CuBr (Cuprous bromide)
At normal conditions CuBr crystallizes in the zincblende structure (γ-CuBr):

space group T2d - F4 3m ,
Work function (γ-CuBr):
φ (polycrystalline) = 7.1(4) eV [74G1]
Bulk plasmon energy ! ωp = 17.7(5) eV [74G1].
Direct band gap at Γ with Eg = 3.077 eV at T = 4K as best value extrapolated from various optical results
[77G]. At room temperature Eg = 2.91eV (at zero pressure) has been derived from experiments studying
the absorption edge under hydrostatic pressure [81V].
For the phase diagram and structural details of high-temperature / high-pressure phases see Landolt-
Börnstein Vol. III/41B and 17b, and [81V, 86B]. For an investigation of the lattice dynamics in
isotopically tailored CuBr see [01S].
Table 5. γ-CuBr. Copper core-level binding energies

Level n=2 n=3
ns1/2 1095.5 121.2
np1/2 951.0 76.3(2)
np3/2 931.2 73.9(2)
Errors ± 0.1 eV unless otherwise stated. If referred to the vacuum level the Cu-ion core levels show a
chemical shift of +1.5(5) eV and are more tightly bound in CuBr than in metallic copper [74G1].
Table 6. γ-CuBr. Occupied valence bands. Critical point energies determined by several authors. All
energy values given in eV with respect to the top of the valence band. Symmetries are indicated in double
(single) group notation.
Critical ARUPS UPS Theory a) Theory c)
Point [93M2] [77G] [80O] [83E]
Γ8 (Γ15) 0 0 0 0
Γ7 (Γ15) –0.8(3) – –0.12 –
Γ8 (Γ12) –2.05(1) –2.1 –1.1 –1.80
Γ8 (Γ15) –4.2(2) –3.3 –3.7 –5.03
Γ7 (Γ15) –4.8(3) – –4.3 –
Γ6 (Γ1) –15.4(3) b) –15.4 b) – –
L4,5,6 –0.8(3) – –0.3 –

L6 –1.4(3) –1.1 –1.8 –0.41
L4,5,6 –2.05(1) –1.8 –1.2 –1.66
L4,5 –4.2(2) –4.1 –3.7 –4.72
L6 –4.7(3) – –4.0 –
L6 –5.6(3) –6.3 –5.1 –7.61
L6 –15.4(3) b) –15.4(3) b) – –
a) Data read from a band structure calculated with the relativistic KKR method in [80O]. b) Taken from [74G1].
c) Calculated by a quasimolecular approach [83E].
102 2.10 Noble metal halides (CuBr) [Ref. p. 156
Table 7. γ-CuBr. Unoccupied bulk conduction band structure. Experimental critical point
energies as obtained from constant-initial-state spectroscopy (CIS) and from secondary
electron emission (SEE) spectra. The energies are referred to the top of the valence band.
CIS [91S] SEE [76L] SEE [93M2] Orbital character [93M2]
7.7(5) 7.5 7.4(2) p
8.9(2) 8.8 8.9(3) s,d
10.2(2) – – s,d
12.0(5) – – ?
14.1(2) – – p,f
15.2(2) – – s,d
17.2(2) – – p,f
The fraction of p-like density of states at the γ-phase valence band edge has been determined both
experimentally and theoretically: The various data range between 28 and 51% [77G], a "best value"
average of the experimental numbers [77G] is 37(5)%.
Figures for 2.10.3
2
10
Br
10
3p
3d
–1
3s
10
4p
–2 4s
10
–3
10
0 200 400 600 800 1000 1200 1400 1600
Fig. 24. CuBr. Atomic subshell photoionization cross sections of bromine

for photon energies from 0 to 1500 eV [85Y]. For atomic copper see Fig. 1
in section 2.9.
3.0 0.5
CuBr CuBr hν = 48.4 eV
0.4
2.5 0.3
0.2
(×3)
2.0 EVBM
0.1
0
1.5 5
hν = 40.8 eV
4
1.0 3
2
(×3) EVBM
0.5 1
EF
0
0 4
hν = 26.9 eV
–11 –9 –7 –5 –3 –1 0 1 3
2
Fig. 25. γ-CuBr. XPS valence band spectrum taken EVBM
from a polycrystalline sample with unmonochromatized 1
MgKα radiation at hv = 1253.6 eV [73K]. See also
0
[74G1]. For the result of a deconvolution which corrects 5
for experimental broadening see [73K]. hν = 21.2 eV
4
3
CuBr 2
EVBM
hν = 24 eV 1
0
6
hν = 16.8 eV
5
4
26
3
2
31 EVBM
1
0
–8 –6 –4 –2 0
36
Fig. 26. γ-CuBr. Photoelectron spectra recorded for
different photon energies from polycrystalline films at
room temperature [74G1]. Dashed lines indicate
estimated secondary electron background [74G1].
41
D C B
A 46 eV ←
EVBM Fig. 27. γ-CuBr. Photoelectron spectra measured at
different photon energies from polycrystalline films
with the sample kept at T = 90 K [91S].
–8 –7 –6 –5 – 4 –3 –2 –1 0 1
3.5
C/B CuBr CuBr
3.0 peak B
Ei = –2.05 eV
2.5
a
Intensity ratio
2.0
peak D
Ei = – 5.63 eV
1.5
peak C b
1.0 Ei = – 4.45 eV
0.5
D/B c
0 6 8 10 12 14 16 18 20 22 24 26 28
10 15 20 25 30 35 40 45 50
Fig. 28. γ-CuBr. Experimental intensity ratios (areas) of Fig. 29. γ-CuBr. Constant initial state (CIS) spectra
peaks labeled B, C and D in Fig. 27 in their dependence referring to photoexcitation out of occupied bands
on photon energy [91S]. labeled B(Ei = –2.05 eV), C(–4.45 eV) and D(–5.63 eV)
in Fig. 27. Polycrystalline film sample kept at T = 90 K
[91S]. The final state energy is referred to the valence
band maximum.
15.0
CuBr CuBr
12.5
Absorption coefficient α [10 cm ]
–1
10.0
5
7.5
5.0
2.5
1 3 5 7 9 11 13 15 17 19 21 0 5 10 15 20 25 30
Final state energy Ef [eV] Photon energy hν [eV]
Fig. 31. γ-CuBr. Absorption spectrum taken from a

Fig. 30. γ-CuBr. Bremsstrahlung isochromat spectrum
polycrystalline sample at liquid nitrogen temperature
(BIS) taken at hν = 1486.6 eV, with the sample holder [72I].
kept at liquid nitrogen temperature [94L]. The energy
was calibrated by the author of this chapter using Fig.
29. It may be accurate to ±1 eV and refers to energy
35
9.07
CuBr
30
8.40 9.62
25 7.75
11.02
6.55 10.55
Reflectivity R [%]
20
13.40
6.05
11.90
5.30 12.25
15
7.22
10
7.01
14.95 Fig. 32. γ-CuBr. Reflection
5 spectrum taken at a sample
temperature T = 6 K [80G2]. All
energies in eV. For data at room
0 temperature see [77L].
5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0
8
CuBr
7
7
6
6
6
5
4
6
3 6
2
Energy E [eV]
1
8 EVBM 8
0
7 6
7 7
4,5
–1 7 6
4,5
8 8
7 6
–2
–3
7 4,5
Fig. 33. γ-CuBr. Energy bands
8 8
calculated along three different k-
–4 6
6 space directions using the
7 7 relativistic KKR method and
–5 6 6 neutral atomic potentials [80O].
See also [88C]. Symmetries given
–6 in double group notation.
Γ X Γ L
Wavevector k
6
CuBr 6
5
6
4
6 6
3
1
Energy E [eV]
8 EVBM 8 EVBM
0
6 4,5
7 7
4,5 6
6
–1 4,5
8 6
6 8 4,5
–2 6
8 4,5
–3
6
8 4,5 7
6 6
–4 7
Fig. 34. γ-CuBr. Energy bands along ΓL calculated
–5 6
using the relativistic KKR method from (a) neutral
atomic potentials and (b) from ionic potentials [80O].
a b Symmetries given in double group notation.
–6
Γ Λ LΓ Λ L
Wavevector k
12.5
CuBr
10.0
7.5
3(3)
5.0
1(3)
1(2)
2.5
EVBM 15(2)
Energy E [eV]
5(2)
0 3(3) 3(2)
3(2) 12(1) 1(2)
– 2.5 5(1)
3(1) 15(1)
1(2)
Fig. 35. γ-CuBr. Semiempirical
– 5.0 energy band structure calculated
3(1) [98B] by fitting tight-binding
– 7.5 eigenvalues to six energies (at Γ, L
and X) obtained from angle-
resolved photoelectron spectra in
– 16 [82W, 83G]. Energy scale referen-
1(1)
1(1) ced to the valence band maximum.
– 18 1(1) Symmetries given in single group
notation. Numbers in brackets
– 20 count bands upward from bottom.
L Γ X
Wavevector k
CuBr

DOS
Fig. 36. γ-CuBr. Density of states

calculated from the semiempirical
band structure shown in Fig. 35
[98B]. Energy scale referenced to
–20 –18 –16 – 6.0 – 4.5 – 3.0 –1.5 0 1.5 3.0 4.5 6.0 valence band maximum.
0 8 EVBM EVBM
6
7
– 0.5 CuBr 4,5
6
– 1.0 4,5
8 6
– 1.5
– 2.0
– 2.5
calculation experiment
– 3.0
– 3.5
8 4,5
6
– 4.0
7
– 4.5
– 5.0 6
– 5.5
– 6.0
Γ Λ L Γ Λ L
Wavevector k
Fig. 38. γ-CuBr. Left panel reproduces part of the calculated band structure shown in Fig. 33 [80O]. Right panel:
corresponding experimental band mapping data obtained from angle-resolved uv-photoemission [93M2]. Symmetries
given in double group notation.
7 CuBr 6+
6+ 6+ 6+
4
2
Energy E [eV]
1 4
+
+
6
0
8– 7+ 6+ 8–
6+
+
–1 7 7
+
8+ 7+ 6+ +
8+ 6+ 4 6– 8+
6– 7
+
+
8
–2 7–
6–
4+
–3 6
+
6–
–4
6+
–5
Wavevector k
Fig. 37. CuBr (rocksalt phase). Relativistic band structure calculated from a standard muffin-tin potential with the
KKR method [81V]. This phase is observed only at high pressures above about 7 GPa [81V]. Symmetries given in
CuBr(111) hν = 21.2 eV CuBr(111)
θ = 20.0°
10.0°
EVBM
7.5°
hν = 40.8 eV
5.0°
2.5°
EVBM
0°
– 4.0 –3.5 –3.0 –2.5 –2.0 –1.5 –1.0 0.5 0 0.5 1.0 1.5
EVBM Initial state energy Ei [eV]
Fig. 40. γ-CuBr (111). Angle-resolved photoelectron

spectra at hν = 40.8 eV for different polar angles θ
–8 –7 –6 –5 – 4 –3 –2 –1 0 1 along the ΓLUX plane of the bulk Brillouin zone, with
the sample at T = 120 K and shielded against visible
light [93M2].
Fig. 39. γ-CuBr (111). Normal-emission photoelectron
spectra taken at two different photon energies. Data
taken while the sample was at T = 120 K and shielded
against visible light [93M2].
110 2.10 Noble metal halides (CuI) [Ref. p. 156
2.10.4 CuI (Cuprous iodide)
At normal conditions CuI crystallizes in the zincblende structure (γ-CuI):

space group T2d - F4 3m ,
Brillouin zone see section 1.3 of this volume.
Work-function (γ-CuI):
φ (polycrystalline) = 6.0(1) eV [74G1]
Bulk plasmon energy ! ωp = 15.1(5) eV [74G1]
Direct band gap at Γ with Eg = 3.12eV at T = 4K as best value extrapolated from various optical results
[77G]. At room temperature Eg = 2.95eV at zero pressure has been derived from experiments studying the
absorption edge under hydrostatic pressure [81V].
For the phase diagram and structural details of high-temperature / high-pressure phases see Landolt-
Börnstein Vols. III/41B and III/17b, and [81V, 86B, 98H]. For the absorption spectra of CuI
nanocrystallites embedded in a glass matrix and the determination of some band parameters of bulk CuI
crystals see [00G] or Landolt-Börnstein, III/34C1, Chap. 6.
Table 8. γ-CuI. Copper core-level binding energies

Level n=2 n=3
ns1/2 1094.4 –
np1/2 951.4 76.8(3)
np3/2 – 74.4(3)
Errors ± 0.1eV unless otherwise stated. If referred to the vacuum level the Cu-ion core levels show a
chemical shift of + 0.8(5)eV and are more tightly bound in CuI than in metallic copper [74G1].
Table 9. γ-CuI. Occupied valence bands. Critical point energies in eV (± 0.1eV if not stated differently in
parentheses) referred to top of valence band. Symmetries are indicated in double (single) group notation.
Symmetry UPS ARUPS Symmetry UPS ARUPS

Point [77G] [88G] Point [77G] [88G]
Γ8 (Γ15) 0 0 X7 – –0.6
Γ7 (Γ15) – –0.6 X6 –1.7 –1.2
Γ8 (Γ12) –2.5 –2.4 X6 –2.2 –2.2
Γ8 (Γ15) –3.1 –3.5 X6,7 –2.5 –2.4
Γ7 (Γ15) – –3.9 X7 – –3.8
Γ6 (Γ1) –13.3(4) – X6 –4.4 –4.2
X6 –6.0 –5.1
X7 (Γ1) –13.3(4) –
The fraction of p-like density of states at the γ-phase valence band edge has been determined
experimentally by several methods [77G], a "best value" average of the data [77G] is 47(5)%.
Ref. p. 156] 2.10 Noble metal halides (CuI) 111
Figures for 2.10.4
2
10
Ι
10
3d
4d 3p
–1 4p
10
3s
–2 5s 5p 4s
10 Fig. 41. CuI. Atomic subshell
photoionization cross sections of
iodine for photon energies from 0
to 1500 eV [85Y]. For atomic
–3 copper see Fig. 1 in section 2.9.
10
0 200 400 600 800 1000 1200 1400 1600
2.5
Cu Ι
2.0
1.5
1.0
0.5
Fig. 42. γ-CuI. XPS valence-band spectrum taken from
0 a polycrystalline sample with unmonochromatized
EF MgKα radiation at hν = 1253.6 eV [73K]. See also
[74G1]. For the result of a deconvolution which corrects
– 0.5 for experimental broadening see [73K].
–11 –9 –7 –5 –3 –1 0 1
0.7 3.5
0.6 CuΙ hν = 48.4 eV CuΙ
3.0
0.5
hν = 76 eV
0.4
(×3) 2.5
0.3
0.2 2.0
0.1
EVBM
0 1.5
6
hν = 40.8 eV
5
1.0
4
(×3)
3 EF
0.5
2
1 0
EVBM 2.5
0
12 hν = 61 eV
hν = 26.9 eV
9 2.0
6
EVBM 1.5
3
0
4 1.0
hν = 21.2 eV
3
2 0.5
EF
1
EVBM 0
0 5
4
hν = 16.8 eV hν = 40 eV
3
4
2
1 3
EVBM
0
–8 –7 –6 –5 –4 –3 –2 –1 0 1
Initial state energy Ei [eV] 2
Fig. 43. γ−CuI. Photoelectron spectra recorded for

different photon energies from polycrystalline films 1
EF
[74G1]. Dashed lines indicate estimated secondary
electron background [74G1].
0
–12 –10 –8 –6 –4 –2 0 2
Fig. 44. γ-CuI. Photoelectron spectra recorded at

different photon energies hv from polycrystalline films
[74I].
→
Fig. 46. γ-CuI. X-ray absorption spectra measured at (a) CuΙ
the Cu K edge, (b) the I L1 edge and (c) the I L3 edge a
[90H]. The energy is referred to the valence band
maximum.
CuΙ
Absorption
b
c
EVBM
EVBM
0 2 4 6 8 10 12 14 16 18 20
Fig. 45. γ-CuI. Bremsstrahlung isochromat spectrum
taken at hv = 1486.6 eV, sample holder kept at liquid
nitrogen temperature [94L]. The energy scale was
calibrated by the author of this chapter using Fig. 1 in 0 10 20 30 40 50
[90H]. It may be accurate to ±1eV and refers to energy Energy E [eV]
35
6.04 CuΙ
8.10
30
6.25 8.45
8.97
6.33
25 4.78
6.48
Reflectivity R [%]
20 9.90
10.55
10.97
11.80
15
12.50
7.62
10
7.17
6.75
5.37
5.10 Fig. 47. γ-CuI. Reflectivity
5 spectrum taken at a sample
temperature of T = 6K [88G]. For
data at room temperature see
0 [77L]. All energies in eV.
5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0
0 15
CuΙ 15 EVBM
∆ 3+ ∆ 4
3
–1 5
∆1 3
1
12 12
–2
∆ 3+ ∆ 4
3 15
–3 15
5
–4
∆1
1 1
–5
Fig. 48. γ-CuI. Band structure
resulting from a semiempirical
–6 LCAO calculation which treats the
matrix elements of the crystal
Hamiltonian as parameters adjust-
– 13
ed to photoemission results
1 1
1 3 [74G1]. Symmetries given in
– 14 single group notation.
L Γ X K Γ
Wavevector k
7 7
7 8
CuΙ 8
6
6
5
7 6
4
3 6 6
2
Energy E [eV]
8 EVBM 8
0
4,5
7 7
7
6
–1 4,5 6
8
7 8 6
–2
–3
8 8 4,5
Fig. 49. γ-CuI. Energy bands
6
–4 6 calculated along three different k-
7 7
space directions using the relati-
6 vistic KKR method and neutral
–5 atomic potentials [80O]. Symme-
6
tries given in double group nota-
–6 tion.
Γ X Γ L
Wavevector k
1.5 CuΙ
1.0
0.5
EVBM 8
0
7
– 0.5
–1.0
Energy E [eV]
–1.5
8
–2.0
–2.5
– 3.0
8
– 3.5
7
– 4.0
– 4.5
– 5.0
L Γ K X Γ
Wavevector k
Fig. 50. γ-CuI. Band structure obtained from the self-consistent relativistic
LMTO-ASA method with "empty spheres" [82B]. Energy referenced to
valence band maximum. Symmetries given in double group notation.
10.0
CuΙ
7.5
3(3)
5.0
1(3) 1(2)
2.5
3(3) EVBM 15(2)

0
Energy E [eV]
5(2)
3(2) 12(1) 3(2) 1(2)

– 2.5
3(1) 5(1)
15(1)
Fig. 51. γ-CuI. Semiempirical
– 5.0
1(2) band structure calculated [98B] by
3(1)
fitting tight-binding eigenvalues to
– 7.5 six energies (at Γ, L and X)
1(1) obtained from angle-resolved
1(1) photoelectron spectra in [82W,
– 13
1(1) 83G]. Energy scale referenced to
the valence band maximum.
– 14 Symmetries given in single group
notation. Numbers in brackets
– 15 count bands upward from bottom.
L Γ X
Wavevector k
CuΙ
DOS
Fig. 52. γ-CuI. Density of states

calculated [98B] from the semi-
empirical band structure shown in
Fig. 51. Energy scale referenced to
valence band maximum.
–14 –13 –12 – 6.0 – 4.5 – 3.0 –1.5 0 1.5 3.0 4.5 6.0
CuΙ
8 +
6
6+
6
+
6
3
4+
2
Energy E [eV]
6+
–
1 8
6+
6+
0 7+ + 4+
7+,8+ 6
+
8 7+ 6+
–1 6 –
7 –
+
6
– 4
–2
6+
–3
6–
–4
+
6
–5
Wavevector k
Fig. 53. CuI (rocksalt phase). Relativistic band structure -relativistic LMTO self-consistent band structure of the
calculated from a standard muffin-tin potential with the high-pressure tetragonal phase of CuI see [86B].
KKR method [81V]. This phase is observed only at Symmetries given in double group notation.
high pressures above about 10 GPa [81V]. For a scalar
6
CuI(110)
CuΙ EVBM Γ8
CuΙ total 0
5
– 0.5
X7 Γ7
– 1.0
DOS [states (atom eV)–1]
4 X6

– 1.5
3 – 2.0
X6 Γ8
– 2.5
2
– 3.0
1 Γ8
– 3.5
EVBM X7 Γ7
0 – 4.0
–7 –6 –5 –4 –3 –2 –1 0 1 X6
Energy E – EVBM [eV] – 4.5
5 – 5.0
d-like X6
– 5.5
4 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5

3 Fig. 56. γ-CuI (110). Initial state energies of dispersing
photoelectron peaks observed in Fig. 55 and
2 interpretation in terms of critical point energies at Γ and
X [88G]. For the resulting empirical energy bands along
1 ΓX and a comparison to experimental optical spectra see
EVBM [88G]. See also [80G2] for earlier work.
0
–7 –6 –5 –4 –3 –2 –1 0 1
3 CuI(110)
CuΙ
p-like
2
1
EVBM
0
–7 –6 –5 –4 –3 –2 –1 0 1
Fig. 54. γ-CuI. From top to bottom: total, partial d and

partial p density of valence states deduced [74G2] from
the photoemission spectra shown in Fig. 43 compared to
those from a semiempirical model calculation using a
parametrized seven-function basis set [74G1]. The
corresponding energy bands are shown in Fig. 48.
Evac
0 1 2 3 4 5 6 7 8 9 10
Electron energy E – Evac [eV]
Fig. 57. γ-CuI (110). Normal-emission electron

spectrum observed after excitation by photons with hv =
40 eV showing secondary electron structures indicated
by arrows located above the vacuum level [88G].
CuI (110)
CuΙ
hν = 34.0 eV
32.0
31.0
30.0
29.0
28.0
27.0
26.0
25.0
24.0
23.0 F
22.0
21.0
20.0
E
D
19.0
18.5 C
18.0 B
17.0
16.5
16.0
15.0 eV
EVBM
–7.0 –6.5 –6.0 –5.5 –5.0 –4.5 –4.0 –3.5 –3.0 –2.5 –2.00 – 1.5 – 1.0 – 0.5 0 0.5 1.0
Fig. 55. γ-CuI (110). Normal-emission photoelectron spectra taken at different photon energies from cleaved single
crystals [88G]. In some curves the arrows indicate secondary electron emission features.
120 2.10 Noble metal halides (AgF) [Ref. p. 156
2.10.5 AgF (Silver fluoride)
At normal conditions AgF crystallizes in the rocksalt structure:

Lattice: fcc, a = 4.936 Å [71M],
space group: O5h – Fm3m,
Brillouin zones: see section 1.3 of this volume.
The fact that silver monofluoride AgF is hygroscopic and highly reactive, together with the existence of
silver subfluoride Ag2F and silver difluoride AgF2 have made it difficult to prepare samples suitable for
photoelectron spectroscopy. This explains why not much experimental data is available for AgF.
Indirect band gap with an exciton energy of Egx = 2.8(3) eV at T = 4.8K [71M], direct exciton transition
energy Egx = 4.63(2) eV at T = 4.8K and assigned to a transition at Γ [71M]. For a comparison of these
numbers with XPS valence–band data see [75M].
Table 10. fcc–AgF. Core–level binding energies in eV relative to EF.
Level n=1 n=2 n=3 Assignment

a b
ns1/2 682.7(2) ) 27.2(6) ) – F in AgF
np1/2 – – 603.1(4) c) Ag in AgF
np3/2 – – 572.3(4) c) Ag in AgF
nd3/2 – – 373.6(2) c) Ag in AgF
nd3/2 – – 374.0(1) Ag in Ag metal
nd5/2 – – 367.6(3) b); 367.8(2) a) Ag in AgF
nd5/2 – – 368.1(1) c) Ag in Ag metal
a b
) [98W]. ) Obtained from data given in [75M].
c
) Obtained from figures in [98W].
Table 11. fcc-AgF. Occupied valence band critical point energies determined
experimentally and from different calculations. Energy values in eV referred to
top of the valence band.
Symmetry XPS a) Theory

Point [72F] [82K]b) [83E]
Γ12 –1.6(4) –1.48 –0.7 –1.27
Γ25' –3.2(1) – –1.9 –1.72
Γ15 –5.3(4) –4.04 –5.3 –1.62
Γ1 –25.8(6) – – –22.3
a) Data obtained from [75M] by assuming that the top of the valence band is located at
1.4 eV below EF.
b) Read from a figure in [82K].
In contrast to AgCl and AgBr, where p-like (halogen) density of states is dominant at the top of the
valence band, the highest valence band of AgF is formed largely by d-like (silver) contribution [75M,
83E].
Ref. p. 156] 2.10 Noble metal halides (AgF) 121
Figures for 2.10.5
10
8
6
4
F
2
1
8
6
4
2
–1 1s
10
8
6
4
2
–2 2s
10
8
6
4
2p
2
–3
10
8 Fig. 58. AgF. Atomic subshell
6
4
photoionization cross sections of
fluorine for photon energies from
2 0 to 1500 eV [85Y]. For atomic
–4 Ag see Fig. 66 in section 2.9.
10
0 200 400 600 800 1000 1200 1400 1600
AgF 0
Ag
AgF AgF
AgF
0
Ag
F
Intensity I
a
610 600 590 580 570 560
Intensity I
Binding energy Eb [eV]

Ag metal
Fig. 60. fcc-AgF. XPS spectrum of the Ag 3p doublet
taken with unmonochromatized MgKα radiation from a
pressed-powder sample of AgF. Energy referred to EF.
F is an Auger line of fluorine [98W].
AgF
b
378 376 374 372 370 368 366 364
Intensity I
Fig. 59. fcc-AgF. XPS spectra of the Ag 3d doublet

taken with unmonochromatized MgKα radiation from
(a) a pressed-powder sample of AgF and (b) Ag metal.
Energies referred to EF [98W]. See [98W] for an XPS
overview spectrum at binding energies between zero
and 1000 eV.
EF
–10 –9 –8 –7 –6 –5 –4 –3 –2 –1 0 1
Fig. 61. fcc-AgF. XPS spectrum taken from a

polycrystalline film with monochromatized (0.5 eV)
AlKα-radiation. Sample kept at 100 K and protected
from exposure to visible light. Energy scale referred to
EF [75M].
Ref. p. 156] 2.10 Noble metal halides (AgF) 123
1.0 1.0
0.9 AgF 0.9 25'
3' 5,3
2'
0.8 0.8
0.7 0.7 5
0.6 1 0.6
3' 3
0.5 0.5
0.4 0.4
0.3 1 0.3
1
0.2 0.2
0.1 1 0.1 1
0 0
–0.1 –0.1
–0.2 –0.2
1
–0.3 –0.3
Energy E [Ry]
Energy E [Ry]
–0.4 –0.4
–0.5 –0.5
3' 12 1 5
–0.6 –0.6
2'
–0.7 –0.7 3' 25' 3 2
–0.8 –0.8
3' 1 5 3' 15
–0.9 12 –0.9 5'
2' 25' 3, 2
–1.0 –1.0
4'
–1.1 –1.1
2'
–1.2 –1.2
3'
–1.3 15 5' –1.3
–1.4 –1.4
–1.5 –1.5
4'
–1.6 –1.6
–1.7 2' –1.7
L Γ X L Γ X
Fig. 62. fcc-AgF. Left panel: self-consistent Hartree-Fock band structure. Right panel: same but with inclusion of
correlation and relaxation corrections [82K]. Symmetries given in single group notation.
16
AgF AgF Ag-like
14
12
DOS [states (eV cell) ]

–1
10
8
DOS
2
EVBM
0
–6 –3 0 3 6 9 12
–8 –7 –6 –5 –4 –3 –2 –1 0 1 a Energy E – EF [eV]
Energy E – EVBM [eV] 10
F-like
Fig. 63. fcc-AgF. Density of valence states calculated
from the band structure shown in the left panel in Fig. 8
62 [82K]. Energy referred to the top of the valence
band.
–1
0
–6 –3 0 3 6 9 12
b Energy E – EF [eV]
16
total
14
12
–1
10
4
→
Fig. 64. fcc-AgF. Partial densities of states for (a) Ag, 2
(b) F and (c) total DOS calculated self-consistently by
the tight-binding LMTO-ASA method [96O]. 0
–6 –3 0 3 6 9 12
c Energy E – EF [eV]
Ref. p. 156] 2.10 Noble metal halides (AgCl) 125
2.10.6 AgCl (Silver chloride)
At normal conditions AgCl crystallizes in the rocksalt structure:

Lattice: fcc, a = 5.5502 Å [55B],
space group: O5h - Fm3m,
Work-function (fcc):
φ (polycrystalline) = 6.3(3) eV [75T]
Indirect optical band gap (from L to Γ) with Eg = 3.2476 eV at T = 1.8K [83N]. The direct gap occurs at Γ
[75M] with Eg = 5.15(5) eV at T = 4K [71C]. For exciton self-trapping in AgCl nanocrystals see [00V].
Table 12. fcc-AgCl. Core-level binding energies in eV referred to the top of the valence band for the
compound and to EF for the metal. All errors are ± 0.1eV unless otherwise stated.
Level n=2 n=3 n=4 Assignment
ns1/2 – – 94.9(3) a) Ag in AgCl

96.8 a) Ag in metal
np1/2 – 601.9a) – Ag in AgCl
np3/2 196.0(3)b) – – Cl in AgCl
np3/2 – 571.0a) – Ag in AgCl
nd3/2 – 372.3a) – Ag in AgCl
nd5/2 – 366.1a) – Ag in AgCl
365.6(3)b) – Ag in AgCl
nd5/2 – 368.3a) – Ag in metal
a) [75T]. b) Data from [75M] but referred to top of valence band.
If referred to the vacuum level, all Ag levels have the same binding energy within ± 0.3eV in both the
halide and the metal. For an interpretation see [75T].
Table 13. fcc-AgCl. Calculated and experimental peak positions in the valence band density of states (in
eV, referred to the top of calculated valence band).
Character Theory [98V] a) XPS [75M] b) UPS [76B2] UPS [74T, 75T]
Cl 3p – 1.0 – 1.4 (4) – 0.8 (2) – 0.6 (2)

Cl 3p – 2.5 – 2.5 (2) – 2.6 (2) – 2.5 (2)
Ag 4d – 3.1 – 3.2 (1) – 3.3 (2) – 3.2 (1)
Ag 4d – 4.6 – 4.4 (2) – – 4.6 (3)
Cl 3s – 15.0 – – – 14.3 (6)
a) Ab initio calculated with self-interaction and relaxation-corrected pseudopotential.
b) Original data [75M] are referred to E . These are shifted rigidly by 1.3 eV to make the comparison with
F
[98V] easier (this brings theoretical and measured top of valence band in direct agreement).
For further calculations see [83E, 97V]. The electronic structure of the states at the bottom of the conduction
band (using an ab initio method) and the corresponding orbital character are calculated in [00O].
126 2.10 Noble metal halides (AgCl) [Ref. p. 156
Figures for 2.10.6
AgCl
T = 83 K
222 K
300 K
Fig. 65. fcc-AgCl. XPS valence

band spectra taken from a
EF
polycrystalline film with mono-
chromatized (0.5 eV) AlKα-radia-
tion at three different temperatures
[75M].
–8 –7 –6 –5 –4 –3 –2 –1 0
6 1
AgCl
1
5
4
1
3
2
Energy E [eV]
1
3
EVBM
4
0
Fig. 67. fcc-AgCl. Band structure
–1 15
1
1 5 3 resulting from a semiempirical
5 1 LCAO calculation which treats the
–2 matrix elements of the crystal
1
12 25' 1,2 3,5 1,2 Hamiltonian as parameters adjust-
–3 3 ed to photoemission results [75T].
5 3
For a different tight-binding band
1 1,4
–4 calculation see [76S1]. Symme-
3 1 tries given in single group
–5 notation.
L Γ X K X
Wavevector k
3.0
AgCl hν = 1486.6 eV
AgCl
2.5
total
EVBM

2.0
hν = 40.8 eV
1.5
1.0
EVBM
0.5
EVBM
hν = 26.9 eV
0
–7 –6 –5 –4 –3 –2 –1 0 1
3.0
d-like
EVBM 2.5
2.0
hν = 21.2 eV
1.5
EVBM
1.0
hν = 16.8 eV 0.5
EVBM
0
–7 –6 –5 –4 –3 –2 –1 0 1
1.5
EVBM p-like
1.0
–7 –6 –5 –4 –3 –2 –1 0 1
Initial state energy Ei [eV] 0.5
EVBM
Fig. 66. AgCl. Photoelectron spectra recorded for
different photon energies from polycrystalline films 0
–7 –6 –5 –4 –3 –2 –1 0 1
[75T]. Energy E – EVBM [eV]
Fig. 68. fcc-AgCl. From top to bottom: total, partial d

and partial p densities of valence states deduced [75T]
from the photoemission spectra shown in Fig. 66
compared to those from a semiempirical model
calculation using a parametrized basis set. The
corresponding energy bands are reproduced in Fig. 67.
9
AgCl
8
1 1
7 1
6
1 1
1
5
4
1
3 1
Energy E [eV]
2
1
3' EVBM
4
0 Fig. 69. fcc-AgCl. Band structure
3
–1 calculated by means of the
1 4
15 1 15 empirical pseudo-potential method
–2 1 5' 1
2' 3
neglecting spin-orbit coupling.
5 4' 3
–3 3 25' 2' 3 25' Energy referred to top of valence
3' 1 1
5 5 2,3
band. The symmetry labels
1 2,3
–4 2' 1 correspond to the origin at the Cl
12 2 12
1 atom [76W]. Symmetries given in
–5 3' 2 1
3 1 4 4 single group notation.
–6
L Λ Γ ∆ X U,K Σ Γ
Wavevector k
13
AgCl
12
–
11 – 4
6
–
10 6
+
7
9
8 6
–
7
–
6
6
+
6
5
Energy E [eV]
1
4
+
6
3 6
+
2
Fig. 70. fcc-AgCl. Band structure
1 calculated by means of the
EVBM 4
+ relativistic KKR method. The
0 + symmetry labels are referred to the
6
– –
8 8 origin at the Ag-atom [81O]. For a
–1 –
semirelativistic band structure
6
– 7 6
–
+
– 6 obtained from a self-consistent
–2 + 6 +
6 7 + + +
8
+ 8 6 ,4 local-density potential with the
+ LMTO-ASA method calculated at
–3 7
+ 7
6
+
+
7
+ 8
+ two different lattice constants see
8
–4 4
+
6
+ [81V]. Symmetries given in
–5
Γ Σ X ∆ Γ Λ L
Wavevector k
1.0 1.0
1 12
0.9 AgCl 2'
5 0.9
2' 15 4'
0.8 0.8
25'
0.7 0.7
2' 5
0.6 3 0.6
3
0.5 0.5
25'
0.4 1 0.4 3
0.3 0.3 3
1
0.2 1 0.2
0.1 0.1 1
1
0 0
Energy E [Ry]
Energy E [Ry]
–0.1 –0.1 1
–0.2 –0.2
–0.3 –0.3
–0.4 –0.4 3'
–0.5 –0.5 15
2' 1
–0.6 –0.6
12 5',3
3'
–0.7 –0.7
3' 2 5
15 3' 25'
–0.8 –0.8
–0.9
2' 51 –0.9
2'
3' 12 4'
–1.0 –1.0
25' 3
–1.1 5 –1.1
3'
–1.2 –1.2
2' 4'
–1.3 –1.3
L Γ X L Γ X
Fig. 71. fcc-AgCl. Left panel: self-consistent Hartree-Fock band structure. Right panel: same but with inclusion of
AgCl
theor.
exp.
DOS
EVBM
Fig. 72. fcc-AgCl. Density of valence states (solid line)
calculated from the band structure shown in the right
panel of Fig. 71 [82K] and compared to the exper-
imental total DOS (dashed line) obtained from
photoemission spectra [75T, 82K].
–7 –6 –5 –4 –3 –2 –1 0
8
7
AgCl
6
5
4
3
2
Energy E [eV]
1
EVBM
0
Fig. 73. fcc-AgCl. Energy bands
–1
calculated by the density-
–2 functional pseudopotential method
[94K]. Zero of energy at the top of
–3 the valence band. For a contour
plot of the valence electron
–4
pseudodensity on a (100) plane
–5 passing through Ag and Cl sites
see also [94K].
–6
L Γ X W K Γ
Wavevector k
6 AgCl
5
4
3
2
1
EVBM
0
–1
Energy E [eV]
–2
–3
–4
–5
–6 Fig. 75. fcc-AgCl. Band structure
calculation employing a full-
– 12 potential linear augmented-Slater-
– 13 type-orbital implementation of the
local-density approximation [97V].
– 14 Energy zero referred to top of the
– 15 valence band.
W L Γ X W K
Wavevector k
21
AgCl Ag-like AgCl calc.
18
15
–1
12
DOS
9
6
EVBM
3
0 exp.
–6 –3 0 3 6 9 12
a Energy E – EF [eV]
5
Cl-like
4
–1
EVBM
2
–8 –7 – 6 –5 – 4 –3 –2 –1 0 1 2
1 Initial state energy Ei [eV]
Fig. 77. fcc-AgCl. Top: bulk density of states calculated

using the energy band structure shown in Fig. 76 [98V].
0
–6 –3 0 3 6 9 12 Bottom: XPS valence band spectrum taken with 0.5 eV
b Energy E – EF [eV] resolution from a polycrystalline film kept at T = 83 K
21 [75M].
total
18
15
–1
12
3
←
Fig. 74. fcc-AgCl. Partial densities of states for (a) Ag,
(b) Cl and (c) total DOS calculated self-consistently by
0 the tight-binding LMTO-ASA method [96O].
–6 –3 0 3 6 9 12
12
AgCl
11
10
6
5
4
3
Energy E [eV]
1
EVBM
0
–1
–2
–3
–4
–5
–6
– 14
– 15
– 16
L Γ X W K Γ
Wavevector k
Fig. 76. fcc-AgCl. Band structure LDA calculation based on self-interaction
and relaxation-corrected pseudopotentials. Spin-orbit coupling is included.
The horizontal dashed lines indicate the experimental energy gap. Energy
referred to top of the valence band [98V]. See also [98N].
Ref. p. 156] 2.10 Noble metal halides (AgBr) 133
2.10.7 AgBr (Silver bromide)
At normal conditions AgBr crystallizes in the rocksalt structure:

Lattice fcc, a = 5.7747 Å [55B]
space group Oh5 - Fm3m,
Work-function (fcc):
φ (polycrystalline) = 6.3 (3) eV [75T].
Indirect optical band gap (from L to Γ) with Eg = 2.6845 eV at T = 1.8 K [84S]. The direct gap occurs at Γ
with Eg = 4.292(2) eV at T = 4.2 K [71C]. Growth, surface structure and phonon dynamics of thin
epitaxial AgBr(100) films grown on NaCl are reported in [99G].
Table 14. fcc-AgBr. Core-level binding energies in eV referred to the top of the
valence band for the compound and to EF for the metal. All errors are ± 0.1 eV unless
otherwise stated.
Level n=3 n=4 Assignment
ns1/2 – 94.9 (3) a) Ag in AgBr
96.8 a) Ag in metal
np1/2 602.0 a) – Ag in AgBr
np3/2 571.3 a) – Ag in AgBr
180.3(3) b) – Br in AgBr
nd3/2 372.4 a) – Ag in AgBr
nd5/2 366.4 a) – Ag in AgBr
365.9(2) b) – Ag in AgBr
368.3 a) – Ag in metal
a) [75T]. b) Data from [75M] but referred to top of valence band.
If referred to the vacuum level, all Ag levels have the same binding energy within ± 0.3 eV in both the
halide and the metal. For an interpretation see [75T].
Table 15. fcc-AgBr. Calculated and experimental peak positions in the valence band density of states (in
eV, referred to the top of the calculated valence band).
Character Theory [98V] a) XPS [75M] b) UPS [74T, 75T] c) PES [90M] UPS[93M1]
Br 4p –1.9 –2.0(4) –2.0(2) –1.4(2), –2.0(2) –1.8(2)

Br 4p –3.1 –3.2(1) –3.1(2) –3.1(2), –4.2(2) –2.8(2)
Ag 4d –4.0 –3.9(1) –3.9(2) –3.9(2) –3.7(2)
Ag 4d –4.9 –4.9(1) –4.9(2) –4.2(5) –4.3(4)
Br 4p ≈–4.9 –5.1(3) –5.2(2) –5.3(3) –4.5(3),
–5.2(2)
Br 4s –15.3 – –15.0(6) – –
a) Ab initio calculated with self-interaction and relaxation-corrected pseudopotential.
b) Original data [75M] are referred to E . These are shifted rigidly by 0.8 eV to make the comparison with [98V]
F
easier (this brings theoretical and measured top of valence band in direct agreement).
c) Shifted rigidly by 0.2 eV. See also [76B2].
For further calculations see [83E, 97V]. The electronic structure of the states at the bottom of the conduction
band (using an ab initio method) and the corresponding orbital character are calculated in [00O].
134 2.10 Noble metal halides (AgBr) [Ref. p. 156
Figures for 2.10.7
AgBr
T = 83 K
190 K
300 K
Fig. 78. fcc-AgBr. XPS valence

band spectra taken from a
EF
polycrystalline film with mono-
chromatized (0.5 eV) AlKα radia-
tion at three different temperatures
[75M].
–8 –7 –6 –5 –4 –3 –2 –1 0
AgBr
Fig. 79. fcc-AgBr. Photoemission of the Br 3d core-

levels excited by photons of hv = 120 eV [91W]. The
sample is a polycrystalline, closed film condensed at
T = 83 K and studied at this temperature. For detailed
studies of its annealing behaviour as well as of samples
deposited at T = 403 K see [91W].
73 72 71 70 69 68 67 66 65
4
AgBr hν = 11.8 eV AgBr hν = 21.2 eV
3
T = 80 K
295 K
2
0
4
hν = 11.6 eV
3
2
EVBM
1
a
0
4
hν = 11.4 eV hν = 40.8 eV
3
1
0
4
hν = 11.2 eV
3
2
EVBM
1
b
0
4
hν = 11.0 eV
3
0
4
hν = 10.8 eV
3
1
c
0 –7 –6 –5 –4 –3 –2 –1 0 1 2
6 7 8 9 10 11 12 Initial state energy Ei [eV]
Energy E [eV]
Fig. 81. fcc-AgBr. Photoelectron spectra taken from
Fig. 80. fcc-AgBr. Photoelectron spectra, normalized to polycrystalline samples at T = 90 K for different photon
incident photon flux, from polycryst-alline samples kept energies (a,b). Trace c reproduces the calculated DOS
at T = 80 K (solid lines) and 295 K (dashed), for different [82K], but shifted in energy to make the sharp peaks at
photon energies hν [76B1]. E is energy above VBM. 3.8 eV coincide [93M1]. For data recorded at RT see
[75T]. Energy scale referred to the experimental VBM.
AgBr hν = 80 eV
(× 33)
EVBM
hν = 100 eV
(× 20)
EVBM
hν = 120 eV
(× 3.75)
EVBM
hν = 140 eV
(× 1)
Fig. 82. fcc-AgBr. Photoelectron

spectra recorded at different
photon energies from poly-
crystalline samples kept at 77 K
[89K]. Since the photon energy
tunes the intensity through the
Cooper minimum around hv = 150
EVBM eV, the intensities are normalized
to equal maximum amplitude
[89K]. See also [90M].
–10.0 –7.5 –5.0 –2.5 0 2.5 5.0

2.0
AgBr
1.5
Asymmetry parameter β
1.0
p/d band Fig. 83. fcc-AgBr. Experimental asymmetry parameter
β( hv) for the angular distribution of photoelectron
0.5 intensities for photon energies moving across the
Cooper minimum around hv = 150 eV [89K]. Filled
circles refer to low lying bands with dominant Ag(4d)
0
partial valence density of states, while open circles
d bands correspond to the upper bands with strong
– 0.5 Ag(4d)/Br(4p) hybridized DOS. Solid (dashed) lines are
drawn to guide the eye. A polycrystalline sample was
used, checked for random orientation and kept at T = 88
–1.0 K [89K].
40 60 80 100 120 140 160 180
13 +
+
7 AgBr 7
12
+ +
8 8
11 6
–
–
4
10
+
7 –
6
9
8
–
6
7
–
6 6
5
Energy E [eV]
+
6
4
3 6
+
+
6
2
1
EVBM 4
+
0 –
8 –
8 +
–
6
–1 6 7
–
– Fig. 84. fcc-AgBr. Band structure

6 +
–2 – 6 calculated by means of the
6 + relativistic KKR method. The
+ 6
8 8
+ +
6 ,4
+
–3 + +
symmetry labels are referred to the
7 7 6
+
origin at the Ag atom [81O].
+
–4 8 7
+
8
+
Symmetries given in double group
+
6 4
+
notation.
–5
Γ Σ X ∆ Γ Λ L
Wavevector k
1.0 1.0
2'
2'
0.9 AgBr 5 0.9
12
0.8 0.8 4'
25' 2'
0.7 0.7 15
0.6 3 0.6 5
3 2'
0.5 0.5
25'
0.4 0.4
1 1
3
0.3 1 0.3 3
0.2 0.2
1
0.1 0.1 1
1
Energy E [Ry]
Energy E [Ry]
0 0
–0.1 –0.1
–0.2 –0.2
3'
–0.3 –0.3 15
–0.4 –0.4
2' 5'
–0.5 –0.5
3' 3' 1
–0.6 –0.6 12 5
15 3'
–0.7 –0.7 25' 3 2
12 2'
–0.8 2' 5' –0.8 4'
–0.9 3' 1 –0.9

5
–1.0 25' 2,3 –1.0
3'
–1.1 2' –1.1
4'
–1.2 –1.2
L Γ X L Γ X
Fig. 85. fcc-AgBr. Left panel: self-consistent Hartree-Fock band structure. Right panel: same but with inclusion of
AgBr
exp.
EVBM
DOS
theor. Fig. 86. fcc-AgBr. Density of valence states (solid line)

calculated from the band structure shown in the right
panel of Fig. 85 [82K] and compared to the
experimental total DOS (dashed line) obtained from
photoemission spectra [75T, 82K].
–7 –6 –5 –4 –3 –2 –1 0
30 ←
AgBr Ag-like Fig. 87. fcc-AgBr. Partial densities of states for (a) Ag,
(b) Br and (c) total DOS calculated self-consistently by
25 the tight-binding LMTO-ASA method [96O].
20
–1
15 For Figs. 88, 89 see next page
10
5
AgBr calc.
0
–6 –3 0 3 6 9 12
a Energy E – EF [eV]
5
Br-like
DOS
4
–1
2
exp.
0
–6 –3 0 3 6 9 12
b Energy E – EF [eV]
30
total
25
20
–1
EVBM
15
–7 – 6 –5 – 4 –3 –2 –1 0 1 2 3
10
Fig. 90. fcc-AgBr. Top: bulk density of states calculated
using the energy band structure shown in Fig. 89 [98V].
5 Bottom: XPS valence band spectrum taken with 0.5 eV
resolution from a polycrystalline film kept at T = 83 K
[75M].
0
–6 –3 0 3 6 9 12
6
AgBr
5
4
3
2
1
EVBM
0
Energy E [eV]
–1
–2
–3
–4
–5
–6 Fig. 88. fcc-AgBr. Band structure
calculation employing a full-
– 12 potential linear augmented-Slater-
– 13 type-orbital implementation of the
local-density approximation [97V].
– 14 Energy with respect to the top of
the valence band.
– 15
W L Γ X W K
Wavevector k
7
6
AgBr
5
4
3
2
1
EVBM
0
Energy E [eV]
–1
–2
–3
–4
–5
–6 Fig. 89. fcc-AgBr. Band structure
LDA calculation based on self-
– 13 interaction and relaxation-correct-
– 14 ed pseudopotentials. Spin-orbit
coupling is included. Energy
– 15 referred to top of the valence band
[98V].
– 16
L Γ X W K Γ
Wavevector k
17.5 2.5
AgBr d-like AgBr calc. 5
d-like
15.0
2.0
4
12.5
DOS [states (eV atom) ]

p-like
–1
–1
DOS [electrons eV ]
–1
1.5
10.0 3
7.5 1.0 2
5.0
0.5 1
2.5 EVBM
0 0 0
2.25
d-like exp.
p-like
2.00
1.75 p-like
DOS [arb. units]
1.50
DOS [electrons eV ]
–1
1.25
1.00
EVBM
0.75
0.50 –7 –6 –5 –4 –3 –2 –1 0 1 2
EVBM
0.25
Fig. 92. fcc-AgBr. Bottom: experimental [93M1] partial
0 p-like and d-like densities of valence states, derived
–7 –6 –5 – 4 – 3 – 2 –1 0 1 from the spectra shown in Fig. 81. Top: calculated
Energy E – EVBM [eV] [90M] partial densities of states (see also Fig. 91) after
convolution with a 0.95 eV (FWHM) Gaussian line
Fig. 91. AgBr. Partial d- and p-densities of valence shape and a rigid shift in energy to make the prominent
states calculated from the band structure of Fig. 85 d-peaks at 3.8 eV coincide [93M1]. For further
[93M3]. experimental results see also [90M] and [75T].
142 2.10 Noble metal halides (AgI) [Ref. p. 156
2.10.8 AgI (Silver iodide)
At normal conditions AgI crystallizes in the γ-(zincblende-) phase which, however, is metastable and
often coexisting with the β-(wurtzite-)phase:
zincblende lattice: a = 6.473 Å [63W], space group T2d - F 4 3m
wurtzite lattice: a = 4.580 Å, c = 7.494 Å [63W], space group C46v - P63mc.
Both phases may coexist up to 420 K. Depending on the deposition conditions, the β-γ mixing ratio of
thin films can be varying between the pure β-phase and a practically pure γ-phase.
Work-function (γ-AgI): φ (polycrystalline) = 6.7(3) eV [74G1].
Direct band gap at Γ with Eg = 2.82 eV [81V] for γ-AgI. Bulk plasmon energy !ωp = 12.6(5) eV [74G1].
The direct gap energy (at Γ) is Eg = 3.025(1) eV for β-AgI at T = 1.6 K [76D].
Under normal pressure AgI crystallizes in the stable α-phase between T = 420 and 831 K. In this phase
the iodine atoms form a bcc lattice, while the two Ag atoms are distributed statistically over 24 lattice
points. In an electric field the Ag atoms can easily migrate. The conductivity is three to four orders of
magnitude larger than in β-AgI. At pressures above 0.7 GPa (at room temperature) AgI goes over to the
rocksalt structure and its optical gap becomes indirect from L to Γ [81V]. For phase diagrams, structural
details and electronic properties of high-temperature/high-pressure phases see Landolt-Börnstein Vols.
III/41B, III/17b, III/22a and [77G, 81V].
Table 16. AgI. Core-level binding energies in eV referred to top of valence band for
the compound and to EF for the metal. All errors are ± 0.1 unless otherwise stated.
Level n=3 n=4 Assignment
ns1/2 717.6(2) 95.7 Ag in AgI a)
719.4(3) 96.8 Ag in metal b)
np1/2 602.7 – Ag in AgI a)
np3/2 571.8 – Ag in AgI a)
nd3/2 373.0 – Ag in AgI a)
nd5/2 367.0 – Ag in AgI a)
367.1(2) – Ag in AgI c)
368.3 – Ag in metal b)
617.3(4) – I in AgI c)
a) For γ-AgI [74G1].
b) [74G1].
c) For γ-AgI [75M].
If referred to the vacuum level, the Ag-ion core levels show a chemical shift of + 0.9 (5) and are more
tightly bound in AgI than in metallic silver [74G1].
Ref. p. 156] 2.10 Noble metal halides (AgI) 143
Table 17. AgI. Calculated and experimental peak positions in the valence band density of states (in eV),
referred to the top of the calculated valence band.
Character Theory [98V] a) XPS [75M] b) UPS [76B2] c) UPS [74G1] d)
I 5p –1.7 –2.3(2) –1.7 –2.1(2)

I 5p –3.9 –  –4.0(1)
–4.4
Ag 4d –5.1 –5.0(1)  –4.9(1)
Ag 4d –5.7 –5.7(1) – –5.7(1)
I 5s –13.4 – – –14.1(6)
a) Ab initio calculated for γ-AgI with self-interaction and relaxation-corrected pseudopotential.
b) β-AgI. Original data [75M] referred to E . These are shifted rigidly by 0.1 eV to make comparison with [98V]
F
easier.
c) β-AgI.
d) γ-AgI. Original data [74G1] shifted rigidly by 0.8 eV to make comparison with [98V] easier. The averaged
fraction of p-like density of states at the γ-phase top of the valence band has been determined as 68% [63C] and
66% [74G1], respectively.
Ab initio electronic structure calculations for all three phases (α, β, γ) of AgI are presented in [97V].
These employ the full-potential linear augmented-Slater-type-orbital implementation of the local-density
approximation. Spin-orbit interaction is not taken into account. Although band-gap magnitudes are
underestimated, their location and relative ordering as well as bandwidths are in good agreement with
experiment.
Figures for 2.10.8
Ag I
Fig. 93. γ-AgI. XPS valence band spectrum taken with

EVBM
unmonochromatized AlKα radiation (hv = 1486.6 eV)
from a polycrystalline film at room temperature. The
arrow indicates the position of the iodine 5s band.
Energy referred to top of valence band [74G1].
– 18 – 15 – 12 –9 –6 –3 0 3
Ag I
Fig. 94. AgI. XPS spectra taken

with 0.5 eV resolution (mono-
chromatized photons at hv =
1486.6 eV) from β-AgI at T = 100
EF K (dotted line) and α-AgI at T =
441 K (solid line). Energy referred
to EF [75M].
–9 –8 –7 –6 –5 –4 –3 –2 –1 0 1
Ag I hω = 30 eV
EVBM
22.5 eV
EVBM
15 eV
Fig. 95. γ-AgI. Photoelectron

spectra taken from a poly-
crystalline film at different photon
EVBM energies hv [74E1]. For spectra at
other photon energies see also
[74E2].
–10 –9 –8 –7 –6 –5 –4 –3 –2 –1 0 1
1.4 0.8
Ag I Ag I hν = 40.8 eV
1.2
0.6
1.0
0.4
Intensity ratio
0.8
0.2
0.6 EVBM
0
0.4 1.8
hν = 26.9 eV
0.2
1.2
EVBM
0 10 20 30 40 50 60 70 80
Electron kinetic energy Ek [eV] 0.6
Fig. 96. γ-AgI. Experimental intensity ratio (areas) of

0
5p-like intensity from iodine (observed at binding
energy 0…3.7 eV, compare Fig. 95) and 4d-like 6
intensity from silver (observed at 3.7…6.0 eV below hν = 21.2 eV
top of valence band, compare Fig. 95) versus electron
kinetic energy [74E2]. 4
2
EVBM
0
10
hν = 16.8 eV
2
EVBM
0
–8 –6 –4 –2 0
Fig. 97. γ-AgI. Photoelectron spectra taken for different

photon energies from polycrystalline films. Dashed
lines indicate estimated secondary electron background
[74G1].
2
Ag I
15 EVBM 15
0
3 ∆ 3+ ∆ 4
5
–2 ∆1
1
12 1 12
–4 3 5
15 15
1
1
–6
–8
– 10
1 3 1
– 12 1
– 14
L Γ X K Γ
Wavevector k
Fig. 98. γ-AgI. Band structure resulting from a semiempirical LCAO

calculation which treats the maxtrix elements of the crystal Hamiltonian as
parameters adjusted to photoemission results [74G1, 77G]. For a modified
tight-binding approach to calculate the band structures and corresponding
densities of states of the AgI polymorphs (fcc, α, β, γ) see [76S2].
Symmetries given in single group notation.
9 ←
Ag I total Fig. 99. γ-AgI. From top to bottom: total, partial d and
8 partial p density of valence states deduced from the
photoemission spectra reproduced in Fig. 97 [74G1].
Histograms show the corresponding DOS from the
7 calculated model bands reproduced in Fig. 98 [74G1].
6
5 For Fig. 100 see next page
3 AgI
1
EVBM
0
–7 –6 –5 –4 –3 –2 –1 0 1
8
d-like
exp.
7
6
DOS
2
calc.
1
EVBM EVBM
0
–7 –6 –5 –4 –3 –2 –1 0 1
3 –6 –5 –4 –3 –2 –1 0 1

p-like
2 Fig. 101. γ-AgI. Upper curve: experimental total density
of states from [74G1]. Histograms: total (dash-dotted
1 line) and partial-p (dotted line) density of valence states
EVBM calculated [77O] from the band structure reproduced in
Fig. 100 [77O]. Energy zero refers to calculated top of
0 valence band. The experimental curve is rigidly shifted
–7 –6 –5 –4 –3 –2 –1 0 1
Energy E – EVBM [eV] in energy to improve visual agreement.
10.5
10.0 AgI 6
9.5 4
8 8
9.0 6
8.5 7 7 6
8.0
7.5
7.0
6.5 7
6.0
5.5 6
6
5.0
4.5
4.0 6
6
Energy E [eV]
3.5
3.0
2.5
2.0
1.5
1.0
0.5
EVBM 8
0 8
4
–0.5
7 7 7
–1.0 6
–1.5 6
–2.0 6
–2.5 6
6 6
–3.0 8 7 8
–3.5 7 6 4
6
–4.0 7 7
6 4
–4.5 8 8
–5.0
Γ Σ X ∆ Γ Λ L
Wavevector k
Fig. 100. γ-AgI. Band structure calculated with the fully relativistic KKR
method employing a muffin-tin potential constructed from neutral atomic
potentials [77O]. Symmetries given in double group notation.
11.0
+ 6–
10.5 7 Ag I 7
+
10.0 + 8
+
8
9.5
9.0
8.5
4–
8.0 +
7 6–
7.5
7.0 6
–
6.5
–
6.0 6
5.5
5.0
4.5
4.0
Energy E [eV]
3.5 +
6 6
+
6
+
3.0
2.5
2.0
1.5
1.0
0.5
EVBM 4+
0
– +
–0.5 8 8– 6
–1.0 –
7
–1.5 + –
7 6 –
6
–2.0 +
6 + 6
–2.5 – + +
6 7 4
–3.0 + + +
8 8 6
–3.5 6+
+ + 7+
–4.0 8 7
6+ 4+
–4.5
–5.0
Γ Σ X ∆ Γ Λ L
Wavevector k
Fig. 102. fcc-AgI. Band structure calculated with the fully relativistic KKR
method employing a muffin-tin potential constructed from neutral atomic
potentials [77O]. Symmetries given in double group notation
Ag I
6–
6
5 6–
6+ 6+
2
1
Energy E [eV]
–1 4+
–
8 +
6
–2
+
7
6–
–3 –
6
6+
–4 6
–
+
6
7+ 6
+
–5 8
+
7
+
6
+ 4+
6+
8+ 7
+
4+
–6
Wavevector k
Fig. 103. fcc-AgI. Relativistic band structure obtained from a standard muffin-tin potential by means of the KKR
method [81V]. Symmetries given in double group notation.
6
5
α-Ag I
4
3
2
1
EVBM
0
Energy E [eV]
–1
–2
–3
–4
–5
–6
– 12
– 13
– 14
Γ H' N' P N H Γ P
a Wavevector k
6
β-Ag I
5
4
3
2
1
EVBM
0
Energy E [eV]
–1
–2
–3
–4
–5
–6
– 12
– 13
– 14
L A Γ M K H
b Wavevector k
Fig. 104 a,b. For caption see next page
6
5
γ- Ag I
4
3
2
1
EVBM
0
Energy E [eV]
–1
–2
–3
Fig. 104. AgI. Band structure
–4
calculations for (a) α-AgI, (b) β-
–5 AgI and (c) γ-AgI. The calculations
–6 employ a full-potential linear
augmented-Slater-type-orbital im-
– 12 plementation of the local-density
– 13 approximation. Energies referred
to the top of the valence band
– 14 [97V].
W L Γ X W K
c Wavevector k
Ag I calc.
DOS
exp.
Fig. 106. β-AgI. Top: bulk density of states calculated

using the energy band structure shown in the left panel
EVBM of Fig. 105 [98V]. Bottom: valence band spectrum
taken with 21.2 eV photons from a polycrystalline film
kept at room temperature [74G1].
–8 –7 –6 –5 – 4 –3 –2 –1 0 1 2
7 7
γ-Ag I β-AgI
6 6
5 5
4 4
3 3
2 2
1 1
EVBM EVBM
0 0
Energy E [Ry]
Energy E [Ry]
–1 –1
–2 –2
–3 –3
–4 –4
–5 –5
–6 –6
–7 –7
– 13 – 13
– 14 – 14
L Γ X W K Γ A L M Γ A H K Γ
Fig. 105. AgI. Left panel shows band structure LDA calculation for γ-AgI (zincblende), based on self-interaction and
relaxation-corrected pseudopotentials. Spin-orbit coupling is included. Right panels show the same for β-AgI
(wurtzite). Energies referred to top of the valence band [98V].
AgI D C hν = 21.2 eV hν = 40.8 eV
T = 251 °C
T = 251 °C
B
A
218 °C
218 °C
149 °C
186 °C
147 °C
139 °C
146 °C
C
D
142 °C D
C EVBM 108 °C
29 °C
A
B B
29 °C A EVBM
–7 –6 –5 –4 –3 –2 –1 0 1 –7 –6 –5 –4 –3 –2 –1 0 1
a Initial state energy Ei [eV] b Initial state energy Ei [eV]
Fig. 107. AgI. Photoelectron spectra collected from a polycrystalline film at various temperatures after excitation
with photons of hv = 21.2 eV (a) and 40.8 eV (b). The shape of the spectra reflects the structural phase transition
from γ-AgI to α-AgI at about T = 147°C [79O].
1.00 1.14
AgI T = 230 °C AgI
0.75 1.12
p-like
1.10
0.50
1.08
0.25
1.06
0
1.00 1.04
T = 147 °C
0.75 1.02
1.00
0.50
0.98 3K
0.25
0.96
0
1.00 0.94
T = 145 °C
0 40 80 120 160 200 240 280
0.75 a Temperature T [°C]
6.4
0.50
0.7
6.3
0.25
0.6
Energy gap Eg(0) – Eg(T ) [eV]

6.2
0
1.00
p-bandwidth [eV]
T = 35 °C 0.5
6.1
0.75 (β + γ ) (α)
0.4
6.0
0.50
0.3
5.9
0.25
0.2
5.8
0 Tc = 147 °C
–7 –6 –5 –4 –3 –2 –1 0
Energy E – EVBM [eV] 0.1
5.7
0 40 80 120 160 200 240 280
Fig. 108. AgI. Partial p-density of valence states b Temperature T [°C]
derived from the photoelectron spectra shown in Fig.
107 [79O]. The temperature dependence reflects the Fig. 109. AgI. The phase-transition from γ-AgI to α-
AgI as reflected in photoemission spectra (compare
phase transition from γ-AgI to α-AgI between T =
Figs. 107, 108). (a) Amplitude ratio of peaks labeled C,
145°C and 147°C [79O].
D in Fig. 107 as a function of temperature (dots). The
solid lines are a guide to the eyes. (b) Experimental
width of the partial p-density of states (see Fig. 108)
versus temperature (dots, left scale) compared to the
change in size of the optical band gap with temperature
(solid line, scale on the right) [79O].
156 2.10 Noble metal halides (References)
55B Berry, C.: Phys. Rev. 97 (1955) 676.

63C Cardona, M.: Phys. Rev. 129 (1963) 69.
63W Wyckoff, R. W. G.: Crystal Structures, Vol. 1, John Wiley and Sons, 1963.
67S Song, K. S.: J. Phys. (Paris) 28 (1967) 195.
71C Carrera, N. J., Brown, F. C.: Phys. Rev. B 4 (1971) 3651.
71M Marchetti, A. P., Bottger, G. L.: Phys. Rev. B 3 (1971) 2604.
71S Sato, S., Ishii, T., Nakagura, I., Aita, O., Nakai, S., Yokota, M., Ichikawa, K., Matsuoka, G.,
Kono, S., Sagawa, T.: J. Phys. Soc. Jpn. 30 (1971) 459.
72F Fowler, W. B.: Phys. Status Solidi (b) 52 (1972) 591.
72H Hanson, R. C., Hallberg, J. R., Schwab, C.: Appl. Phys. Lett. 21 (1972) 490.
72I Ishii, T., Sato, S., Matsukawa, T., Skaisaka, Y., Sagawa, T.: J. Phys. Soc. Jpn. 32 (1972) 1440.
72K1 Kono, S., Ishii, T., Sagawa, T., Kobayasi, T.: Phys. Rev. Lett. 28 (1972) 1385.
72K2 Kennedy, D. J., Manson, S. T.: Phys. Rev. A 5 (1972) 227.
73C Calabrese, E., Fowler, W. B.: Phys. Status Solidi (b) 57 (1973) 135.
73K Kono, S., Ishii, T., Sagawa, T., Kobayasi, T.: Phys. Rev. B 8 (1973) 795.
73S Sugiura, C.: Phys. Rev. B 8 (1973) 823.
74E1 Eastman, D. E., Grobman, W. D., Freeouf, J. L., Erbudak, M.: Phys. Rev. B 9 (1974) 3437.
74E2 Eastman, D. E.: in: Vacuum Ultraviolet Radiation Physics, Koch, E. E., Haensel, R., Kunz, C.,
(eds.), Pergamon-Vieweg, 1974, p. 417.
74G1 Goldmann, A., Tejeda, J., Shevchik, N. J., Cardona, M.: Phys. Rev. B 10 (1974) 4388.
74G2 Goldmann, A., Tejeda, J., Shevchik, N. J., Cardona, M.: Solid State Commun. 15 (1974) 1093.
74I Ishii,T., Kono, S., Matsukawa, T., Sagawa, T., Kobayashi, T.: J. Electron Spectrosc. Relat.
Phenom. 5 (1974) 559.
74K1 Kono, S., Kobayasi, T.: Solid State Commun. 15 (1974) 1421.
74K2 Kemeny, P. C., Poole, R. T., Jenkin, J. G., Liesegang, J., Leckey, R. C. G.: Phys. Rev. A 10
(1974) 190.
74T Tejeda, J., Braun, W., Goldmann, A., Cardona, M.: J. Electron Spectrosc. Relat. Phenom. 5
(1974) 583.
74W Williams, D. R., Jenkin, J. G., Leckey, R. C. G., Liesegang, J.: Phys. Lett. 49 A (1974) 141.
75M Mason, M. G.: Phys. Rev. B 11 (1975) 5094.
75T Tejeda, J., Shevchik, N. J., Braun, W., Goldmann, A., Cardona, M.: Phys. Rev. B 12 (1975)
1557.
76B1 Bauer, R. S., Lin, S. F., Spicer, W. E.: Phys. Rev. B 14 (1976) 4527.
76B2 Bauer, R. S.: Phys. Rev. B 14 (1976) 4539.
76D Dinges, R., Fröhlich, D., Uihlein, Ch.: Phys. Status Solidi (b) 76 (1976) 613.
76L Lin, S. F., Spicer, W. E., Bauer, R. S.: Phys. Rev. B 14 (1976) 4551.
76S1 Smith, P. V.: J. Phys. Chem. Solids 37 (1976) 581.
76S2 Smith, P. V.: J. Phys. Chem. Solids 37 (1976) 589.
76W Shy-Yih Wang, J., Schlüter, M., Cohen, M. L.: Phys. Status Solidi (b) 77 (1976) 295.
77G Goldmann, A.: Phys. Status Solidi (b) 81 (1977) 9.
77K Khan, M. A.: Phys. Lett. 61A (1977) 421.
77L Lewonczuk, S., Gross, J. G., Khan, M. A., Ringeissen, J.: Phys. Status Solidi (b) 83 (1977)
161.
77O Overhof, H.: J. Phys. Chem. Solids 38 (1977) 1214.
78C Copperthwaite, R. G., Steinberg, M.: Solid State Commun. 28 (1978) 915.
78P Potts, A. W., Lyus, M. L.: J. Electron Spectrosc. Relat. Phenom. 13 (1978) 305.
79D Doran, N. J., Woolley, A. M.: J. Phys. C.: Solid State Phys. 12 (1979) L321.
79F Farberovich, O. V., Akopdzhanov, R. G., Kurganskii, E. P., Domashevskaya, E. P.: Sov. Phys.
Solid State 21 (1979) 1691.
79G Gross, J. G., Lewonczuk, S., Khan, M. A., Ringeissen, J.: Solid State Commun. 30 (1979) 181.
79K1 Kunz, A. B., Weidman, R. S.: J. Phys. C.: Solid State Phys. 12 (1979) L371.
79K2 Kleinmann, L., Mednick, K.: Phys. Rev. B 20 (1979) 2487.
2.10 Noble metal halides (References) 157
79L Lamoureux, M., Farnoux, F. C.: J. Phys. (Paris) 40 (1979) 545.

79O Ostrow, M., Goldmann, A.: Phys. Status Solidi (b) 95 (1979) 509.
79P Pong, W., Okada, S. K.: Phys. Rev. B 20 (1979) 5400.
79V Van der Laan, G., Sawatzky, G. A., Haas, C., Myron, H. W.: Phys. Rev. B 20 (1979) 4287.
79Z Zunger, A., Cohen, M. L.: Phys. Rev. B 20 (1979) 1189.
80B Berkowitz, J., Batson, C. H., Goodman, G. L.: J. Chem. Phys. 72 (1980) 5829.
80G1 Gross, J. G., Lewonczuk, S., Khan, M. A., Pinchaux, R., Ringeissen, J.: Solid State Commun.
35 (1980) 445.
80G2 Gross, J. G., Lewonczuk, S., Khan, M. A., Ringeissen, J.: Solid State Commun. 36 (1980) 907.
80H Herman, F., Kasowski, R. V.: private communication.
80M McNaughton, R. M., Allen, J. D., Schweitzer, G. K.: J. Electron Spectrosc. Relat. Phenom. 18
(1980) 363.
80O Overhof, H.: Phys. Status Solidi (b) 97 (1980) 267.
80W Westphal, D., Goldmann, A.: Solid State Commun. 35 (1980) 441.
81F Farberovich, O. V., Timoshenko, Y. K., Bugakov, A. M., Domashevskaya, E. P.: Solid State
Commun. 40 (1981) 559.
81O Overhof, H.: private communication. [Fig. 70 is reproduced from Landolt-Börnstein III/22a,
1987, p. 447].
81V Ves, S., Glötzel, D., Cardona, M., Overhof, H.: Phys. Rev. B 24 (1981) 3073.
82B Blacha, A., Cardona, M., Christensen, N. E., Ves, S., Overhof, H.: Solid State Commun. 43
(1982) 183.
82F1 Fröhlich, D., Volkenandt, H.: Solid State Commun. 43 (1982) 189.
82F2 Farberovich, O. V., Timoshenko, Y. K., Bugakov, A. M., Domashevskaya, E. P.: Sov. Phys.
Solid State 24 (1982) 349.
82G Glötzel, D.: private communication.
82K Kunz, A. B.: Phys. Rev. B 26 (1982) 2070.
82M Mellander, B. E.: Phys. Rev. B 26 (1982) 5886.
82R Ren, S. Y., Allen, R. E., Dow, J. D., Lefkowitz, I.: Phys. Rev. B 25 (1982) 1205.
82W Westphal, D., Goldmann, A.: J. Phys. C.: Solid State Phys. 15 (1982) 6661.
83B Blacha, A., Vers, S., Cardona, M.: Phys. Rev. B 27 (1983) 6346.
83E Ermoshkin, A. N., Evarestov, R. A., Kuchinskii, S. A., Zakharov, V. K.: Phys. Status Solidi (b)
118 (1983) 191.
83G Goldmann, A., Westphal, D.: J. Phys. C.: Solid State Phys. 16 (1983) 1335.
83L Lewonczuk, S., Gross, J. G., Ringeissen, J., Khan, M. A., Riedinger, R.: Phys. Rev. B 27
(1983) 1259.
83N Nakamura, K., von der Osten, W.: J. Phys. C: Solid State Phys. 16 (1983) 6669.
84C Christensen, N. E.: Phys. Status Solidi (b) 123 (1984) 281; 125 (1984) K59.
84G Guimaraes, P. S., Parada, N. J.: J. Phys. C.: Solid State Phys. 17 (1984) 1695.
84P Podloucky, R.: J. Phys. Chem. Solids 45 (1984) 609.
84S Sliwczuk, U., Stolz, H., von der Osten, W.: Phys. Status Solidi (b) 122 (1984) 203.
85Y Yeh, J. J., Lindau, I.: Atomic Data and Nuclear Data Tables 32 (1985) 1.
86B Blacha, A., Christensen, N. E., Cardona, M.: Phys. Rev. B 33 (1986) 2413.
86E Edamatsu, K., Ikezawa, M., Tokailin, H., Takahashi, T., Sagawa, I.: J. Phys. Soc. Jpn. 55
(1986) 2880.
86S Samson, J. A. R., Shefer, Y., Angel, G. C.: Phys. Rev. Lett. 56 (1986) 2020.
87E Ebbsjö, I., Vashishta, P., Dejus, R., Sköld, K.: J. Phys. C 20 (1987) L441.
88C Cardona, M., Christensen, N. E., Fasol, G.: Phys. Rev. B 38 (1988) 1806.
88G Gross, J. G., Fliyou, M., Lewonczuk, S., Ringeissen, J., Pinchaux, R.: Phys. Rev. B 37 (1988)
3068.
88H Hamilton, J. F.: Adv. Phys. 37 (1988) 359.
89K Kwawer, G. N., Miller, T. J., Mason, M. G., Tan, Y., Brown, F. C., Ma, Y.: Phys. Rev. B 39
(1989) 1471.
90E Enderby, J. E., Barnes, A. C.: Rep. Progr. Phys. 53 (1990) 85.
158 2.10 Noble metal halides (References)
90H Hamza, S., Khan, M. A., Lewonczuk, S., Ringeissen, J., Petiau, J., Sainctavit, Ph.: Solid State
Commun. 75 (1990) 29.
90M Mason, M. G., Tan, Y. T., Miller, T. J., Kwawer, G. N., Brown, F. C., Kunz, A. B.: Phys. Rev.
B 42 (1990) 2996.
91S Skonieczny, J., Lodders, F., Engelhard, H., Goldmann, A., Johnson, R. L. Ghijsen, J.: Z. Phys.
B: Condens. Matter 85 (1991) 211.
91W Wagner, M. K., Hansen, J. C., deSouza-Machado, R., Liang, S., Tobin, J. G., Mason, M. G.,
Brandt, S., Tan, Y. T., Yang, A.-B., Brown, F. C.: Phys. Rev. B 43 (1991) 6405.
93K Kapecki, J., Rodgers, J.: in: Kirk-Othmer Encyclopedia of Chemical Technology, Howe-Grant,
M., (ed.), 4th edition, Vol. 6, Wiley, New York 1993.
93M1 Matzdorf, R., Goldmann, A.: J. Electron Spectrosc. Relat. Phenom. 63 (1993) 167.
93M2 Matzdorf, R., Skonieczny, J., Westhof, J., Engelhard, H., Goldmann, A.: J. Phys.: Condens.
Matter 5 (1993) 3827.
93M3 Mason, M. G.: private communication of results obtained by A. Barry Kunz (unpublished).
Details of calculation are reported in [90M].
94K Kirchhoff, F., Holender, J. M., Gillan, M. J.: Phys. Rev. B 49 (1994) 17420.
94L Lewonczuk, S., Ringeissen, J., Beaurepaire, E., Khan, M. A.: Phys. Rev. B 49 (1994) 2344.
96N Nakahigashi, K., Tamura, J., Ishibashi, H.: J. Phys.: Condens. Matter 8 (1996) 5295.
96O Onwuagba, B. N.: Solid State Commun. 97 (1996) 267.
97V Victoria, R. H.: Phys. Rev. B 56 (1997) 4417.
98B Bouhafs, B., Heireche, H., Sekkal, W., Avurag, H., Ferkat, M., Certier, M.: Phys. Status Solidi
(b) 209 (1998) 339.
98G Göbel, A., Ruf, T., Cardona, M., Lin, C. T., Wrzesinski, J., Steube, M., Reimann, K., Merle, J.-
C., Joucla, M.: Phys. Rev. B 57 (1998) 15183.
98H Hull, S., Keen, D. A., Hayes, W., Gardner, N. J. G.: J. Phys.: Condens. Matter 10 (1998)
10941.
98K Kondo, S., Itoh, T., Saito, T.: Phys. Rev. B 57 (1998) 13235.
98N Nunes, G. S., Allen, P. B., Martins, J. L.: Solid State Commun. 105 (1998) 377.
98T Tanaka, S., Kamada, M.: J. Electron Spectrosc. Relat. Phenom. 88-91 (1998) 689.
98V Vogel, D., Krüger, P., Pollmann, J.: Phys. Rev. B 58 (1998) 3865.
98W Wolan, J. T., Hoflund, G. B.: Appl. Surf. Sci. 125 (1998) 251.
99E Edamatsu, K., Hisakawa, K., Itoh,T.: Phys. Rev. B 59 (1999) 15868.
99G Glebov, A. L., Panella, V., Toennies, J. P.: Phys. Rev. B 60 (1999) 2046.
99O Ohmura, H., Nakamura, A.: Phys. Rev. B 59 (1999) 12216.
99Z Zhao, J., Masumoto, Y.: Phys. Rev. B 60 (1999) 4481.
00G Gogolin, O., Mshvelidze, G., Tsitsishvili, E., Schmidt, M., Hepting, A., Klingshirn, C.,
Kamilli, A., Send, W., Gerthsen, D.: Phys. Rev. B 62 (2000) 13053.
00O Overhof, H., Gerstmann, U.: Phys. Rev. B 62 (2000) 12585.
00V Vogelsang, H., Husberg, O., Köhler, U., von der Osten, W., Marchetti, A. P.: Phys. Rev. B 61
(2000) 1847.
01S Serrano, J., Ruf, T., Widulle, F., Lin, C. T., Cardona, M.: Phys. Rev. B 64 (2001) 045201.
Ref. p. 337] 2.11 Nonmagnetic transition metals (Introduction) 159
2.11 Nonmagnetic transition metals
2.11.1 Introduction
Transition metals are a group of elements which exhibit valence d-shells filled only partially with
electrons. There are eight 3d transition metals: Sc, Ti, V which are nonmagnetic and the magnetic
elements Cr, Mn, Fe, Co and Ni. The five magnetic transition metals are treated separately in Landolt-
Börnstein Vol. III/23c2 and are therefore not under further consideration in the present chapter. Then we
have eight 4d transition metals: Y, Zr, Nb, Mo, Tc, Ru, Rh and Pd. Among these Tc is not easily
accessible for experimental work since it is radioactive and no stable isotope exists. Finally we have
seven transition metals with outer 5d-shells: Hf, Ta, W, Re, Os, Ir and Pt. Formally also the rare earth
elements La to Lu have 5d orbitals which can be filled with an electron. However, the Lanthanides are
treated separately in Landolt-Börnstein Vol. III/23a and, most important, their relevant physical properties
are in general determined by the 4f electron shell. Therefore the present chapter is confined to Sc, Ti, V
with 3d electrons, the 4d-shell metals Y to Pd and the elements with partially filled 5d-shell ranging from
Hf to Pt. In all of these materials, the physical properties of both the bulk and the surface are largely
determined by the partially filled valence d-shell.
The nd transition elements (n = 3, 4, 5) elements exhibit a wide variety of structural and
electromagnetic properties. For detailed bulk structure data, including phase transitions and other changes
with temperature, we refer to Landolt-Börnstein Vols. III/6 and III/14a. A key factor in the understanding
of transition metals is the peculiar nature of their electronic energy bands. The valence states may be
considered to arise from the nearly degenerate nd- and (n+1)s atomic levels. Their orbitals have different
spatial distribution, with the s electrons generally extending beyond the corresponding d-shell. Already
early studies of photoemission from d-band metals examined, to which extent experimental spectra may
be explained within the one-electron band theory [74S1]. This is of relevance since transition metals are
considered a class of materials in which electronic correlations considerably influence the excitation
spectrum as well as ground-state properties [94U]. Moreover, the hexagonal-close-packed (hcp) structure
is the most common among the transition metals, and this crystal structure is more complex than that of
the cubic metals. The combination of the uniaxial symmetry and the two atoms per unit cell results in an
electronic structure which is also more complex than that of the cubic metals [75J1]. Furthermore,
deviations from the ideal c/a ratio of 1.63 may impose anisotropies, which make band calculations even
more difficult [88B]. In addition, there is no doubt that the heavier elements require the use of a fully
relativistic description. There is no clear consensus, however, regarding the form in which relativity has
to be implemented into an electronic energy band calculation [00T1]. Several transition metals show
structural phase transitions at elevated temperatures [71L, 88L] and the theoretical prediction of phase
stability trends is of considerable interest [00G]. Theoretical ab initio studies of optical properties in the
ultraviolet energy range are still very rare. The reason is that very accurate band structure calculations are
required in a wide energy range, and the problem is complicated by the need to compute a full dielectric
matrix [01K1]. Finally some transition metals are of interest since they show high superconducting
transition temperatures (as compared to their neighbours) as well as anomalies in their phonon dispersion
curves. These metals are often also building blocks in transition-metal compounds having both theoretical
and technological importance.
In the context of photoemission and related spectroscopies with their extreme surface sensitivity it is
not only the three-dimensional bulk band structure and its change with subsequent filling of the d-bands
which attracted considerable interest. In general, transition metal surfaces show high chemical and/or
catalytic activity due to the presence of unfilled d-states around the Fermi level. The d-holes may provide
an easy escape channel for electron transfer from an adsorbate thereby allowing for strong bonds. In
consequence interest, both experimentally and theoretically, is focused to occupied as well as to empty
bands. Moreover, electronic surface properties may be of crucial relevance for surface reactions. For
example, surface core level shifts reflect the difference in potential at the surface and in the bulk due to
the modified structural environment. Thus, while the present chapter concentrates on electronic bulk
properties, we have also included some experimental data concerning surface states and core-level shifts
160 2.11 Nonmagnetic transition metals (Introduction) [Ref. p. 337
where considered necessary or unavoidable: both surface and bulk properties often appear simultaneously
in photoelectron spectra. A comprehensive treatment of surface properties is, however, not within the
scope of the present chapter. Such information can be found elsewhere in Landolt-Börnstein volumes.
Details on surface crystallography and structural parameters, referring to ideal surfaces as well as to
surface reconstruction and relaxation, are collected in Vol. III/24A. Extensive summaries of data
concerning the electronic structure of transition metal surfaces are available in Vol. III/24B and in Vol.
III/24D.
With respect to metals crystallized in the hcp structure we remember the fact that alternative
coordinate systems are used in the literature to describe the hexagonal lattice. Some authors use a
coordinate system referring to the three primitive basis vectors: two axes in the hexagonal plane with an
angle of 60° between them, and the third axis normal to the hexagonal plane. The alternative system uses
four components: three axes in the hexagonal plane with angles of 120° between them, and the fourth axis
normal to the hexagonal plane. In consequence e.g. the D-direction normal to the hexagonal plane
(compare Fig. 10 and 11 in chapter 1.3 of the present volume) is labeled [0001] in the four-axes system
and [001] in the alternative one and similarly [11 2 0] equals [110]. For more details we refer to the
appendix (on Bravais lattices, primitive unit cells, reciprocal lattices and first Brillouin zones) of Landolt-
Börnstein Vol. III/13c. Both index systems are in use and in the data section we left the labels given by
the respective authors to make comparison with the original literature easier.
Ref. p. 337] 2.11 Nonmagnetic transition metals (Sc) 161
2.11.2 Sc (Scandium) (Z = 21)
Lattice hcp, a = 3.309 Å, c = 5.273 Å, c/a = 1.594 [71L]

Electronic configuration: (Ar) 3d1 4s2
Work-function [95H]:
φ (poly) = (3.5 ± 0.3) eV
Table 1. Sc. Core-level binding energies in eV

relative to EF [95H]. Typical scatter between
various sources is ± 0.5 eV. See also [95M].
Level n=2 n=3
ns1/2 498.0 51.1
np1/2 403.6
28.3
np3/2 398.7
Table 2. Sc. Occupied valence bands. Experimental and theoretical determination of high symmetry point
energies. Energy values are given in eV w.r. to EF.
Point Level Experiment Theory
[94P1] [91M] [80S1] * [76D]
Γ Γ1+ – 4.65(10) – 5.1 – 6.3 – 5.1
Γ4– – 1.85(10) – 1.6 – 1.0 – 1.6
* taken from a figure.
162 2.11 Nonmagnetic transition metals (Sc) [Ref. p. 337
Figures for 2.11.2
10
2 Sc
10
1
2p
–1
2s
10
3p
10
–2 3s
–3 4s
10
3d
10−4
0 200 400 600 800 1000 1200 1400
Photon energy hn [eV]
Fig. 1. Sc. Atomic subshell photoionization cross sections for photon

energies from 0 to 1500 eV [85Y].
LMM 2p 3/2
Sc
2p 1/2
2s
Intensity I
LMM
I
3p
Ar Ar 3s
940 Eb [eV] 870
1200 1000 800 600 400 200 EF = 0

Fig. 2. Sc. Overview XPS spectrum. Insert shows blow-up of the Sc

(LMM) Auger-electron spectrum [95M]. Data taken with
unmonochromatized MgKα radiation. For results obtained with
monochromatized AlKα radiation see [95M].
2p 3/2
Sc Sc
3p
2p 1/2
3s
Intensity I
P
Intensity I
425 415 405 395 60 50 40 30 20

Binding energy E b [eV] Binding energy E b [eV]
Fig. 3. Sc. XPS spectrum showing 2p core levels and Fig. 4. Sc. XPS spectrum showing 3s and 3p core levels
plasmon satellite (P) from polycrystalline film excited taken from poly-crystalline film with unmono-
with unmonochromatized MgKα radiation [77G]. See chromatized AlKα radiation. Feature P is dominated by
also [95M]. Eb w.r. to EF bulk plasmon excitation, but contains also a weak
contribution from excitation of the 3s core level by the
AlKα3,4 satellite[77G].
Sc (0001) Sc
Intensity I
Intensity I
38 36 34 32 30 28 26 −12 −8 −4 EF= 0
Fig. 5. Sc (0001). 3p core levels for normal (filled Fig. 6. Sc. XPS spectrum of the valence band obtained
circles) and 60° off-normal (empty symbols) emission. with monochromatized (0.5 eV) AlKα radiation (hν =
Photon energy hν = 80 eV [92B]. 1487 eV) [77L1].
Sc Sc
Intensity I
Intensity I
DOS
0 50 100 150
Fig. 7. Sc. Photoionization cross section of the 3d valence
band for a polycrystalline film in its dependence on 0
photon energy, measured at an initial state energy 0.5 eV
below EF by CIS spectroscopy [85B]. 0 2 4 6 8 10
Sc 3d Fig. 8. Sc. Top: Experimental bremsstrahlung
E i [eV]
M 2,3 isochromat spectrum (photon energy hν = 1486.7 eV,
44.25
total resolution 0.7 eV). Bottom: Calculated density of
43.25 states. Dashed without broadening, solid line including
42.25 broadening to simulate instrumental and lifetime widths
40.25 [84S].
38.25
36.25
34.25
Intensity I
32.25
30.25 Sc A
29.25
28.25
27.25 θ = 45° B
26.25
M 2,3 A
24.25
22.25 C
B
30°
20 30 40 50
C A
Intensity I
Fig. 9. Sc. Inverse photoemission spectra taken for a 15°

polycrystalline film in normal electron incidence at
various electron energies Ei, showing strong variation in B
the 3d features (tick marks). Fermi level indicated by C
arrows [89H]. 0° A
→ B
Fig. 10. Sc. Inverse photoemission spectra for a
polycrystalline film taken at electron incidence angles θ
and (resonant) electron energy Ei = 42.25 eV. Peaks A,
EF
B and C reflect Sc3d empty-state features, the
fluorescent decay of the Sc3p core hole, and plasmon- 20 30 40
related effects, respectively [88H]. Photon energy hν [eV]
6+ 4 4
6+ 2 1 1 1
5+ 1 1 Sc 1
4 3 2 1,3
1+ 5 1 1
1+ 1 2- 1 4’
1+ 4 4 2,4
6- 2
3 2 1- 3
6 3 2
6- 1 1,3 2’
1 2
1 3’
3 3 4-
0.6 1 2 6 3 1
1 1 1,3
2 2+
3 2 1 1’
E F = 0.493Ry 3
Energy E [Ry]
1 1
3+ 2’
4-
4
4-
5 2
0.4 2
1
2- 2
2 3 4’
3+ 1 1 3+
1 1
1+ 1’
1,3
2
0.2
1 1
1 1
1+ 1
0 1+
Γ∆A S H P K T Γ Σ MUL R A L S’ H’ M T’ K’
Wavevector k
Fig. 11. Sc. Band structure calculated by the KKRZ method in
conjunction with a quantum defect method [80S1]. See also [76D].
Symmetry labels in single group notation
0.7
Sc
0.5
Energy E [Ry]
EF
0.3
s p d total
0.1
− 0.1
3 1.5 0 3 0 30 0 60 0 Γ M K Γ A L H A M L K H
DOS Wavevector k
Fig. 12. Sc. Right panel: Energy bands calculated self-consistently by means of the full potential linearized
augmented-plane-wave method [88B]. See also [91M]. Left panel: Density of states with s,p,d orbital character (in
states/Ry/atom) and corresponding total DOS (states/Ry/unit cell) [88B].
10
Sc
dz 2 EF
dxy, dx 2- y 2
dxz , d yz
DOS [states/atom/Ry]
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Energy E [Ry]
Fig. 13. Sc. Symmetry decomposition of the partial d-density of
states (normalized to one d-state without degeneracy) resulting from
the energy bands shown in Fig. 12 [88B].
1.0
Sc
0.8
0.6
Reflectivity R
0.4
0.2
0 1 2 3 4 5
Fig. 14. Sc. Experimental normal-incidence
reflectivity data taken from single crystals with
electric field vector E parallel (solid line) and
perpendicular (dashed line) to the c-axis [81W2].
Sc(0001) exp. calc.

h ν [eV]
50
48
46
44
42
40
Intensity I
38
36
34
32
30
28
26
24
22
20
−5 −4 −3 −2 −1 0 = EF −5 −4 −3 −2 −1 0 = EF
Fig. 15. Sc(0001). Experimental (left) and calculated (right) results for photo-electron normal emission, i.e. along the
ΓA direction of the bulk Brillouin zone, at various photon energies hν. P-polarized light is incident at 30° with
respect to the surface normal [94P1]. See also [92B].
Sc(0001)
θ = 60°
50° θ = 50°
40° 40°
30° 30°
20° 20°
Intensity I
Intensity I
10° 10°
0° 0°
−10° −10°
−20° −20°
−30° −30°
−4 −3 −2 −1 0 = EF −4 −3 −2 −1 0 = EF
Fig. 16. Sc(0001). Off-normal photoemission spectra taken along the ΓK (left) and ΓM (right) azimuths. Photon
incidence at 30° with respect to surface normal. Photon energy hν = 40 eV [92B].
0 Sc (0001) 0
−1 −1

−2 −2
−3 −3
−4 −4
−5 −5
M K Γ K M K M Γ M Γ
Wavevector kII Wavevector kII
Fig. 17. Sc(0001). E(k||) values derived from data in Fig. 16 [92B].
Sc (0001)
α
= 80°
70°
Intensity I
60°
50°
40°
30°
20° Fig. 18. Sc(0001). Photoelectron spectra collected at
polar angle θ = 20° in the ΓM direction as a function of
10°
photon incidence angle α. Photon energy hν = 40 eV,
0° electric field vector confined to the ΓM mirror plane,
i.e. α = 0 corresponds to fully s-polarized light [94P1].
−5 −4 −3 −2 −1 0 = EF
Ref. p. 337] 2.11 Nonmagnetic transition metals (Ti) 169
2.11.3 Ti (Titanium) (Z = 22)

See also [71L] for other phases
Electronic configuration: (Ar) 3d2 4s2
φ (poly) = (4.3 ± 0.3) eV
Table 3. Ti. Core-level binding energies in eV

relative to EF [95H]. Typical scatter between various
sources is ± 0.5 eV. See also [95M].
Level n=2 n=3
ns1/2 560.9 58.6
np1/2 461.2
32.6
np3/2 453.7
For core-hole lifetime broadenings see [92F]. For a measurement of the Kβ-to-Kα X-ray intensity ratio
and the resulting valence electron configuration see [02R1].
Figures for 2.11.3
10
2 Ti
10
3d
1
2p
2s
–1
10
3p
–2 3s
10
–3 4s
10
3d
10−4
0 200 400 600 800 1000 1200 1400
Fig. 19. Ti. Atomic subshell photoionization cross sections for photon
170 2.11 Nonmagnetic transition metals (Ti) [Ref. p. 337
2p 3/2
Ti
LMM
2p 1/2
2s
Intensity I
3p
3s
Ar Ar
1200 1000 800 600 400 200 EF = 0

Fig. 20. Ti. Overview XPS spectrum. Data taken with

unmonochromatized MgKα radiation. For spectrum excited with
Ti 2p 3/2 Ti
453.8
2p 1/2
Intensity I
Intensity I
6.15
470 460 450 −12 −8 −4 EF= 0

Fig. 21. Ti. XPS data showing region of the spin-orbit- Fig. 22. Ti. XPS spectrum of the valence band obtained
split 2p core levels taken with unmonochromatized with monochromatized (0.5 eV) AlKα radiation (hν =
MgKα radiation [79W]. See also [83P] and [95M]. 1487 eV) [77L1].
Ti Ti
Intensity I
Intensity I
(a )
( b)
(c )
−8 −6 −4 −2 EF= 0 0 50 100 150

Fig. 23. Ti. Angle-integrated UPS data from a Ti(0001) Fig. 24. Ti. Photoionization cross section of the 3d
surface using photon energies hν = 16.8 eV (a), 21.2 eV valence band for a polycrystalline film in the photon
(b) and 40.8 eV (c) [80F1]. energy range between 15 and 150 eV, measured by CIS
spectroscopy (initial state energy 0.5 eV below EF )
[85B]. See also [96K].
Ti h ν [eV]
Ti 22.5
20.4
Intensity I
18.7
Intensity I
15.7
14.5
0 12.7
11.1
DOS
0 = EF 2 4 6 8
Energy E [eV]
Fig. 26. Ti. Bremsstrahlung isochromat spectra taken at
0
different photon energies hν from polycrystalline
sample [92P].
0 2 4 6 8 10
Fig. 25. Ti. Top: Experimental bremsstrahlung

isochromat spectrum (photon energy 1486.7 eV, total
resolution 0.7 eV). Bottom: Calculated DOS. Dashed
without broadening, solid line including broadening to
simulate instrumental and lifetime widths [85S]. See
also [82R].
172 2.11 Nonmagnetic transition metals (Ti) [Ref. p. 337
0.8
Ti
0.6
EF
Energy E [Ry]
0.4
0.2 s p d total
0
3 1.5 0 2 0 25 0 60 0 Γ M K Γ A L H A M L K H
DOS Wavevector k
Fig. 27. Ti. Right panel: Energy bands calculated self-consistently by means of the full potential linearized APW
method. Left panel: corresponding s,p,d (states/Ry/atom) and total densities of states (states/Ry/unit cell) [88B]. See
also [75J2] and [87L].
64 11.2 64 11.2
α −Ti (hcp) ω −Ti (hex)
56 9.8 56 9.8
48 8.4 48 8.4
DOS [ electron states/atom/Ry]
NOS [electrons/atom]
40 7.0 40 7.0
32 5.6 32 5.6
24 4.2 24 4.2
16 2.8 16 2.8
8 EF 1.4 8 EF 1.4
0 0 0 0
0 0.06 0.12 0.18 0.24 0.30 0.36 0.42 0.48 0 0.06 0.12 0.18 0.24 0.30 0.36 0.42 0.48
Energy E [Ry] Energy E [Ry]
Fig. 28. Ti. Electronic densities of states (left scale) and integrated number of electrons (right scale) calculated for the
α-phase (hcp, left panel) and the ω-phase (simple hexagonal, right) using the nonrelativistic APW method [79V2].
For experimental data see [78F] and [79V2].
Ti
1.5
s
DOS [states/eV/ atom]
1.0 p
d
Intensity I
0.5
EF
BG
0
−10 −8 −6 −4 −2 0 = EF 2 −10 −8 −6 −4 −2 0 = EF 2
Fig. 29. Ti. Comparison of the XPS valence band spectrum (right, dots) with a simulated one (right, solid line) using
a partial DOS calculation (left) after inclusion of several broadening mechanisms [81H2]. BG: estimated secondary
electron background.
1.0 ←
Ti Fig. 30. Ti. Experimental normal-incidence reflectivity
data [81W1] obtained from different experiments. For
0.8 details and tables of the "most recommended" data see
[81W1].
0.6 10
Reflectivity R
Ti
0.4 8
0.2 6
10 ε 2
0 4
5 10 15 20 25 30 ε2
2
Ti ε2
10
0
5 10 15 20 25 30
Fig. 31. Ti. Experimental ε2 spectra [81W1] from
hν [eV] different experiments. See also caption to Fig. 30.
Intensity I
47
←
Fig. 32. Ti. Angle-integrating UPS spectra taken from a
Ti(0001) surface showing resonant electron emission:
37 (top) spectrum on resonance (hν = 47 eV) and (bottom)
off-resonance (hν = 37 eV) [83B2].
−15 −10 −5 0 = EF
174 2.11 Nonmagnetic transition metals (V) [Ref. p. 337
2.11.4 V (Vanadium) (Z = 23)
Lattice bcc, a = 3.024 Å [71L]

Electronic configuration: (Ar) 3d34s2
φ (poly) = (4.3 ± 0.3) eV
Table 4. V. Core-level binding energies in eV

Level n=2 n=3
ns1/2 626.7 66.3
np1/2 519.8
37.2
np3/2 512.1
For core-hole lifetime broadenings see [92F]. For a measurement of the Kβ-to-Kα X-ray intensity ratio
and the resulting valence electron configuration see [02R1].
Figures for 2.11.4
10
2 V
10
3d
1
2p
2s
–1
10
3p
–2
3s
10
3d
–3
4s
10
10−4
0 200 400 600 800 1000 1200 1400
Fig. 33. V. Atomic subshell photoionization cross sections for photon

Ref. p. 337] 2.11 Nonmagnetic transition metals (V) 175
2p 3/2
V LMM
I
LMM
2p 1/2 795 785 775
Eb [eV]
Intensity I
Fig. 34. V. Overview XPS spectrum.

2s
The insert shows a blow-up of the
V(LMM) Auger-electron spectrum
[95M]. Data taken with
3p unmonochromatized MgKα radiation.
3s
Ar Ar Spectrum excited with mono-
chromatized AlKα is shown in [95M].
1200 1000 800 600 400 200 EF = 0
2p 3/2 V (100) Intensity I

V
3p
Intensity I
2p 1/2
3s
507 512 517 522 527 532 80 70 60 50 40 30

Fig. 35. V. XPS spectrum of the 2p levels taken with Fig. 36. V. Photoemission from the 3p and 3s core
unmonochromatized MgKα radiation from a V(100) levels taken with hν = 130 eV [92S].
surface after background subtraction [94V]. See also
[79W], [86R] and [95M]. V
Intensity I
Fig. 37. V. XPS spectrum of the valence band obtained

with monochromatized (0.5 eV) AlKα radiation [77L1].
See also [82A2].
−12 −8 −4 EF= 0
h ν [eV] V V
52
A
48
Intensity I
Intensity I
−20 − 16 − 12 −8 −4 0
h ν [eV]
0 50 100 150
64 Photon energy hν [eV]
58
54 Fig. 39. V. Photoionization cross section of the 3d
Intensity I
50 valence band for a polycrystalline film in its

48
46 dependence on photon energy, measured at an initial
45 A state energy 0.5 eV below EF by CIS spectroscopy
44 A
A
43 [85B].
42 A
41 A
40 A
39 A
38 A
−10 −8 −6 −4 −2 0 = EF
Fig. 38. V. Photoemission spectra taken at different V

photon energies hν from a polycrystalline film sample
[92S]. The large enhancement near EF with increasing
hν is due to resonant photoemission. Label A indicates
Intensity I
contribution from an Auger process [92S].
0
DOS
Fig. 40. V. Top: Experimental bremsstrahlung

isochromat spectrum (hν = 1486.7 eV, total resolution
0.7 eV). Bottom: calculated density of states. Dashed
without broadening, solid line including broadening to 0
simulate instrumental and lifetime widths [84S].
0 2 4 6 8 10 12
V V
50
h ν [eV]
22.5
40
20.4
DOS [ states Ry −1]

18.7 30
15.7
20
Intensity I
14.5
12.7
11.1 10
EF
−1.0 −0.8 −0.6 −0.4 −0.2 0 0.2 0.4
Energy E [Ry]
Fig. 43. V. Density of states calculated from the band
structure reproduced in Fig. 42 [78L].
0 = EF 2 4 6 8 10
Energy E [eV]
Fig. 41. V. Bremsstrahlung isochromat spectra taken at
different photon energies hν from polycrystalline
sample [92P].
0.1
V
0 4 3
− 0.1 1 1
3 25’
25’ 3
2
−0.2 4 2 4
4
12 12
2’ 3 3 1 3 3
−0.3 1 1 1 1
5 3 1’
25’
EF 3
Energy E [Ry]
−0.4 1’ 1
1
25’
3
−0.5 2 4
2 4 3 2
2
4 4
−0.6 3
1 1
12 1 1 12
−0.7 1
1
−0.8 1 Fig. 42. V. Energy bands along some
lines of high symmetry in the bulk
1 Brillouin zone calculated using a self-
−0.9
1 consistent LCAO method [78L].
−1.0 Symmetry labels in single group
Γ ∆ H G N D P Λ Γ Σ NP F H notation.
Wavevector k
60 40
V
50
DOS [ electron states /atom / Ry]

30
DOS [ electron states /atom / Ry]
40
30 20
20
10
10
EF
EF
0 0
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Fig. 44. V. Density of states calculated from a band the lowest six bands. Right: Calculated at reduced
structure based on a self-consistent APW method with lattice constant a = 0.95 a0, interpolation of the lowest
exchange parameter α = 2/3. Left: Calculated at normal four bands [72P].
room temperature lattice constant a0 , interpolation of
V 10
25
EF 8
20
15 6
10 4
total
DOS [ states/Ry /atom /spin]
5 2
0 0
20
15
10 d :Γ12
5
0
10
5 d :Γ25’
0
4 p
0
4 s
0
0.2 0.4 0.6 0.8 1.0 1.2 1.4
Energy E [Ry]
Fig. 45. V. Density of states (top panel) and partial s,p,d densities of
states calculated from a self-consistent APW band structure
calculation using the exchange approximation with α = 2/3 [77B].
1.0 20
V
V 20
0.8
ε2
15
10
0.6
Reflectivity R
0 1 2 3
hν [eV]
10
0.4
5
0.2
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Photon energy hν [eV] Photon energy hν [eV]
Fig. 46. V. Experimental normal-incidence reflectivity Fig. 47. V. Experimental ε2 spectra [81W1] from
data [81W1] obtained from different experiments. For different experiments. See also caption to Fig. 46.
details and tables of the "most recommended" data see
[81W1].
10000
V (100) V (100)
θ = 50°
45°
8000
40°
Intensity I
6000 35°
30°
4000
0 25°
20°
−8 −6 −4 −2 0 = EF 2
Initial state energy E i [eV] 2000 15°
10°
Fig. 48. V(100). Normal-emission photoelectron
0°
spectrum taken at hν = 21.2 eV [96P1]. For results from
polycrystalline sample at hν = 21.2 eV see [82A2]. 0
−10 −8 −4 −2 EF= 0
Fig. 49. V(100). Valence band photoemission spectra
recorded at hν = 21.2 eV at different electron emission
angles θ varied in the (01 1 ) plane by sample rotation
about the [011] axis [94P2].
Γ M
V (100) h ν = 11.5 eV
V (100)
EF
0
h ν = 10 eV
Intensity I
−2
0 = EF 2 4 6
H G N Energy E [eV]
Wavevector k
Fig. 51. V(100). Normal-incidence inverse
Fig. 50. V(100). Energy dispersion along Γ-Σ-M of the photoelectron spectra taken at two different photon
surface Brillouin zone, derived from data shown in Fig. energies hν in the isochromat mode [96P1].
49 and compared to the calculated bulk band dispersion
from [72P].
V (100)
θ = 45°
30°
Intensity I
15°
0°
Fig. 52. V(100). Inverse photoemission spectra
recorded in the isochromat mode at photon energy hν =
11.5 eV for various electron incidence polar angles
indicated [96P1].
0 = EF 2 4 6 8
Energy E [eV]
V (100)
E i = 32.2 eV
29.5
26.9
Intensity I
25.2
23.7
20.9
19.7 eV
−2 −1 0 = EF 1 2 3 4 5 6 7 8
Energy E [eV]
Fig. 53. V(100). Normal-incidence inverse photoemission spectra
taken at different incident electron energies Ei [96O].
V (100)
E i = 28.4 eV
26.9
Intensity I
25.2
23.7
22.7
20.9 eV
8 9 10 11 12 13 14 15 16 17 18
Energy E [eV]
Fig. 54. V(100). Normal-incidence inverse photoemission spectra
taken at different incident electron energies Ei [96O]. Energy with
respect to EF.
182 2.11 Nonmagnetic transition metals (Y) [Ref. p. 337
2.11.5 Y (Yttrium) (Z = 39)

Electronic configuration: (Kr) 4d1 5s2
φ (poly) = (3.1 ± 0.3) eV
Table 5. Y. Core-level binding energies in eV

Level n=3 n=4
ns1/2 392.0 43.8
np1/2 310.6 24.4
np3/2 298.8 23.1
nd3/2 157.7 –
nd5/2 155.8 –
Table 6. Y. Occupied valence bands. Experimental and theoretical

determination of high symmetry point energies (given in eV w.r. to EF).
[87B1] [88B] [91M]
Γ Γ1+ – –4.9 –4.8
Γ4– –1.7 –1.9 –1.8
Ref. p. 337] 2.11 Nonmagnetic transition metals (Y) 183
Figures for 2.11.5
10
2 Y
10
3d
1 3p
3d 3p
–1
10
3s
–2 4d 4s 4p
10
–3 4d
10
5s
10−4
0 200 400 600 800 1000 1200 1400
Fig. 55. Y. Atomic subshell photoionization cross sections for photon

10
Y
1
–1
10
–2
10
0 50 100 150 200 250 300 350
Fig. 56. Y. Atomic 4d-subshell cross section near the Cooper

minimum [85Y].
3d 3/2 3d 5/2
Y
3p 3/2
3p 1/2
MNN 3s
Intensity I
Ar
Fig. 57. Y. Overview XPS spectrum.
Data taken with unmonochromatized
4p MgKα radiation [95M]. See also
4s [95M] for spectrum excited by
monochromatized AlKα radiation.
1200 1000 800 600 400 200 EF = 0
Y (0001) Y
Intensity I
Intensity I
0
DOS
30 28 26 24 22 20
Fig. 58. Y(0001). 4p core level spectrum taken with

0
photon energy hν = 60 eV in normal (solid line) and
off-normal (dashed, 60° w.r. to surface normal)
emission geometry [89B, 92B]. 0 2 4 6 8 10
Fig. 59. Y. Top: Experimental bremsstrahlung

isochromat spectrum (hν = 1486.7 eV, total resolution
0.7 eV). Bottom: Calculated DOS. Dashed without
broadening, solid line including broadening to simulate
instrumental and lifetime widths [84S].
Y EF
DOS
Fig. 60. Y. Density of states calculated using the self-

−6 −4 −2 0 2 4 6 consistent ASW method [84S].
0.8
Y
0.6
Energy E [Ry]
0.4 EF EF
0.2
s p d total
0
3 1.5 0 2 0 15 0 40 0 Γ M K Γ A L H A M L K H
DOS Wavevector k
Fig. 61. Y. Right panel: Energy band structure calculated self-consistently by means of the full potential linearized APW-
method. Left panel: corresponding partial (in states/Ry/atom) and total (states/Ry/unit cell) densities of states [88B].
2
0
EF
Energy E [eV]
−1
−2 Γ4 −
−3
−4 Y
Fig. 62. Y. Self-consistent LMTO-
−5 Γ1+ ASA band structure calculation [92B].
A L M Γ K H A Γ
Wavevector k
Y
5
total
s
p
4
DOS [states eV −1]
0
−5 −4 −3 −2 −1 0 1 2
Fig. 63. Y. Total and partial densities of valence states calculated

with the bandstructure shown in Fig. 62 [92B].
1.0
3
total d Y Y
2
E II c 10 R
1 0.8 T
E c
0
2 d − eg 0.6
Reflectivity R
E II c
1
0.4 T
0 E c
3
d − t2g
2 0.2
1
0
−6 −4 −2 0 2 4 6 0 5 10 15 20 25 30
Energy E − E F [eV] Photon energy hν [eV]
Fig. 64. Y. Partial d-like DOS in the bcc phase. Energy Fig. 65. Y. Experimental normal-incidence reflectivity
zero at EF [00G]. data [81W1] obtained with light polarization vector E
parallel (solid line) and perpendicular (dashed) to the c-
axis of the sample.
20
T
E c
Y
E II c
10 ε 2
15
T
E c E II c
10
scale change
0 2 4 8 12 16 20 24
Fig. 66. Y. Experimental ε2 results [81W1] obtained with linearly

polarized light. See legend to Fig. 65 for details.
h ν [eV] = 50
Y(0001)
h ν [eV] 48
= 60
46
44
55
42
50 40
38
45 36
Intensity I
Intensity I
34
40
32
30
35
28
30
26
25 24
Y(0001) 22
20
−14 −12 −10 −8 −6 −4 −2 0 = EF −4 −3 −2 −1 0 = EF
Fig. 67. Y(0001). Photoemission spectra at normal Fig. 68. Y(0001). Normal-emission photoelectron
emission taken for various photon energies hν [87B1]. spectra taken for various photon energies hν [92B].
Y(0001)
T = 340 K
Y(1120)
Intensity I
600
610
620
630
640 K Fig. 69. Y. Photoemission spectra recorded at photon
energy hν = 40 eV in normal-emission geometry from
(top) Y(0001) at room temperature and from Y(11 2 0)
−12 −10 −8 −6 −4 −2 0 = EF at various temperatures as indicated [92B].
Y(0001)
θ = 30°
θ = 30°
20°
20°
10°
10°
Intensity I
Intensity I
0°
0°
−10°
−10°
−20°
−20°
−30° −30°
−4 −3 −2 −1 0 = EF −4 −3 −2 −1 0 = EF
Fig. 70. Y(0001). Angle-dependent photoelectron spectra recorded for hν = 40 eV for electron emission along the ΓK
(left) and ΓM (right) azimuths, resp. [92B].
0 0
−1 −1

−2 −2
−3 −3
−4 −4
Y (0001)
−5 −5
M K Γ K M K Γ M Γ M Γ
Wavevector kII Wavevector kII
Fig. 71. Y(0001). E(k||) values derived from the spectra shown in Fig. 70 [92B].
Y(0001) h ν [eV] = 17 h ν [eV] = 23

Y(0001)
22
16
21
15
20
Intensity I
Intensity I
14
13 19
12
18
0 = EF 2 4 6 8
0 = EF 2 4 6 8 10
Energy E [eV]
Energy E [eV]
Fig. 72. Y(0001). Isochromat normal-incidence inverse
Fig. 73. Y(0001). Normal-incidence isochromat inverse
photoemission spectra taken over the photon energy
photoemission spectra taken over the photon energy
range 12-17 eV [91B, 92B].
range 18-23 eV. Tick marks indicate the onset of
fluorescence due to the decay of a 4p core hole [91B].
190 2.11 Nonmagnetic transition metals (Zr) [Ref. p. 337
2.11.6 Zr (Zirconium) (Z = 40)

φ (poly) = (4.1 ± 0.3) eV
Table 7. Zr. Core-level binding energies in eV

Level n=3 n=4
ns1/2 430.3 50.6
np1/2 343.4 28.5
np3/2 329.7 27.7
nd3/2 181.2 –
nd5/2 178.8 –
Figures for 2.11.6
10
2 Zr
10
3d
3p
1
3d 3p
–1
10
3s
4p
–2
10 4s
4d
–3
10
5s
10−4
0 200 400 600 800 1000 1200 1400
Fig. 74. Zr. Atomic subshell photoionization cross sections for photon
Ref. p. 337] 2.11 Nonmagnetic transition metals (Zr) 191
Zr
10
–1
10
Fig. 75. Zr. Atomic 4d-subshell cross

section near the Cooper minimum
–2
10 [85Y].
0 50 100 150 200 250 300 350
Zr
Intensity I
Fig. 76. Zr. Partially angle-integrated photoionization

cross section for the 4d subshell taken from
polycrystalline sample: experimental data (open circles)
and result of calculation taking solid-state effects into
account [83A].
50 100 150 200
MNN
Zr 3d 5/2
3d 3/2
I
MNN
1120 1105 1090 3p 3/2
Eb [eV]
3p 1/2
Intensity I
3s Fig. 77. Zr. Overview XPS spectrum.

The insert shows the Zr (MNN)
Auger-electron spectrum [95M]. Data
Ar
taken with unmonochromatized MgKα
4p radiation. Spectra with mono-
4s chromatized AlKα are shown in
[95M].
1200 1000 800 600 400 200 EF = 0
Zr 3d 5/2 Zr
178.7
3d 3/2
Intensity I
Intensity I
2.4
193 183 173 −3 −2 −1 0 = EF 1

Fig. 78. Zr. XPS spectrum showing the region of the Fig. 80. Zr. Photoemission at hν = 21.2 eV from
spin-orbit-split 3d core levels taken with polycrystalline sample [87N]. For data taken at hν = 80
unmonochromatized MgKα radiation [79W]. See also eV see [83A].
[95M].
Zr
s EF
1.5 p
d
DOS [states/eV⋅atom]
Intensity I
1.0
0.5
BG
0
−10 −8 −6 −4 −2 0 = EF 2 −10 −8 −6 −4 −2 0 = EF 2
Fig. 79. Zr. Right (data): XPS spectrum of the valence broadening mechanisms) the XPS spectrum shown as a
band obtained with monochromatized (0.6 eV) solid line through the data points. BG = estimated
AlKα radiation [81H2]. Left: Partial densities of s,p,d- secondary electron background [81H2]. See also
like valence states used to calculate (including several [79V1].
h ν [eV]
Zr Zr = 22.5
20.4
Intensity I
18.7
15.7
Intensity I
0
14.5
12.7
11.1
DOS
0 2 4 6 8 10 0 = EF 2 4 6 8 10
Energy E − E F [eV] Energy E [eV]
Fig. 82. Zr. Bremsstrahlung isochromat spectra taken at
Fig. 81. Zr. Top: Experimental bremsstrahlung
isochromat spectrum (photon energy 1486.7 eV, total different photon energies hν from polycrystalline
resolution 0.7 eV). Bottom: Calculated DOS without sample [92P].
broadening (dashed) and (solid line) broadened to
1.0 20
Zr Zr
0.8
15
10 ε 2
0.6
Reflectivity R
10
0.4 ε2
5
0.2
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Photon energy hn [eV] Photon energy hν [eV]
Fig. 83. Zr. Experimental normal-incidence reflectivity Fig. 84. Zr. Experimental ε2 spectrum [81W1]. See also
data obtained from different experiments [81W1]. For legend to Fig. 83.
details and tables of "most recommended" data see
[81W1].
64 11.2 64 11.2
α − Zr (hcp) ω − Zr (hex)
56 9.8 56 9.8
48 8.4 48 8.4

40 7.0 40 7.0
32 5.6 32 5.6
24 4.2 24 4.2
16 2.8 16 2.8
EF
8 EF 1.4 8 1.4
0 0 0 0
0 0.06 0.12 0.18 0.24 0.30 0.36 0.42 0.48 0 0.06 0.12 0.18 0.24 0.30 0.36 0.42 0.48
Fig. 85. Zr. Electronic densities of states (left scale) and integrated number of electrons (right scale) calculated for the
α-phase (hcp, left panel) and the ω-phase (simple hexagonal, right) using the nonrelativistic APW method [79V2].
For experimental data see [79V2].
0.9
Zr
0.7
EF
Energy E [Ry]
0.5
0.3
s p d total
0.1
3 1.5 0 1.5 0 15 0 35 0 Γ M K Γ A L H A M L K H
DOS Wavevector k
Fig. 86. Zr. Electronic band structure (right panel) calculated self-consistently by means of the full potential
linearized APW method and (left panel) partial s,p,d-like densities of states (in states/Ry/atom) and total DOS
(states/Ry/unit cell), respectively [88B]. See also [75J1, 84C2, 87L].
3
Zr
2 total d
1
0
2
d − eg
1
0
3
2 d − t2g
1
0
−6 −4 −2 0 2 4 6
Fig. 87. Zr(bcc). Calculated total and d-like partial

densities of states [00G].
196 2.11 Nonmagnetic transition metals (Nb) [Ref. p. 337
2.11.7 Nb (Niobium) (Z = 41)
Lattice bcc, a = 3.299 Å [71L]

φ (poly) = 4.3 eV
φ (001) = 4.02 eV
φ (110) = 4.87 eV
φ (111) = 4.36 eV
Table 8. Nb. Core-level binding energies in eV

different sources is ± 0.5 eV. See also [95M].
Level n=3 n=4
ns1/2 466.6 56.4
np1/2 376.1 32.6
np3/2 360.6 30.8
nd3/2 205.0 –
nd5/2 202.3 –
Table 9. Nb(110). Energy of critical points above EF determined in different calculations and
experimentally using inverse photoemission. Energies in eV with respect to EF [88J2].
[88J2] [77E] [83S] [87S]
Γ Γ25' 1.6 0.52 0.19 0.43
Γ12 3.5 3.45 3.18 2.72
For theoretical studies of electron and hole quasiparticle lifetimes see [02Z].
Ref. p. 337] 2.11 Nonmagnetic transition metals (Nb) 197
Figures for 2.11.7
2 Nb
10
4d
10 3d
3p
1
3d 3p
–1
10 3s
4p
–2 4s
10
4d
–3
10
5s
−4
10
0 200 400 600 800 1000 1200 1400
Fig. 88. Nb. Atomic subshell photoionization cross sections for

photon energies from 0 to 1500 eV [85Y].
Nb
10
–1
10
–2
10
0 50 100 150 200 250 300 350
Fig. 89. Nb. Atomic 4d-subshell cross section near the Cooper
minimum [85Y].
MNV
Nb 3d 5/2
MNV I 3d 3/2
1100 1085 1070

Eb [eV] 3p 3/2
Intensity I
3p 1/2
3s
Fig. 90. Nb. Overview XPS spectrum

taken with unmonochromatized MgKα
4p radiation. The insert shows a blow-up
4s of the MNV Auger electron spectrum
[95M]. For data with mono-
1200 1000 800 600 400 200 EF = 0 chromatized AlKα see [95M].
Nb Nb
VB
Intensity I
Intensity I
4p
×5
210 208 206 204 202 200 40 30 20 10 EF = 0

Fig. 91. Nb. XPS spectrum of the 3d core level doublet Fig. 92. Nb. XPS spectra of valence band (VB) and 4p
taken with monochromatized (0.6 eV) AlKα radiation core levels [81H2] taken with monochromatized (0.6
from a polycrystalline sample [81H2]. See also [95M]. eV) AlKα radiation.
Nb (001) S2 B Nb
S1
EF
h ν = 240 eV
Intensity I
Intensity I
h ν = 250 eV
−12 −10 −8 −6 −4 −2 0 2 4
Fig. 94. Nb. XPS valence band spectrum from

polycrystalline sample taken with monochromatized
(0.5 eV) AlKα -radiation [76H1].
204.0 203.5 203.0 202.5 202.0 201.5 201.0
Fig. 93. Nb(001). High-resolution 3d5/2 core level

photoemission spectra taken at two different photon
energies hν. Solids circles: experimental data. Solid
lines: fit with three identical Doniach-Sunjic line shapes
convoluted with a Gaussian function and background
curve, where S1, S2 and B denote surface, subsurface Nb
and bulk components [95L].
Intensity I
Nb
h ν [eV] =120
0
100
Intensity I
DOS
80
60
0
−5.0 −2.5 0 = EF 0 2 4 6 8 10
Initial state energy E i [eV] Energy E − E F [eV]
Fig. 95. Nb. Photoelectron spectra from a Fig. 96. Nb. Top: Experimental bremsstrahlung
polycrystalline sample taken at different photon isochromat spectrum (photon energy 1486.7 eV, total
energies hν [82M]. resolution 0.7 eV). Bottom: Calculated DOS without
1.0
Nb Nb
h ν [eV]
= 22.5
0.8
20.4
18.7 0.6
Reflectivity R
15.7
0.4
Intensity I
14.5
12.7
0.2
11.1
0 5 10 15 20 25 30
Fig. 98. Nb. Experimental normal-incidence reflectivity
data obtained from different experiments [81W1]. For
4 6 8 10 details and tables of the "most recommended" data see
0 = EF 2
[81W1].
Energy E [eV]
Fig. 97. Nb. Bremsstrahlung isochromat spectra taken
at different photon energies hν from polycrystalline
sample [92P].
20
Nb 10ε 2
20 Nb EF 10
NOS [electrons / atom]

16 8
15 12 6
8 4
DOS [states /(Ry ⋅ atom ⋅ spin)]
4 total
2
10 0 0
12
ε2
8
4
5 d − Γ12
0
12
8
0 5 10 15 20 25 30 4 d − Γ25’
0
Fig. 99. Nb. Experimental ε2 spectra [81W1] from 2 p
different experiments. See also legend to Fig. 98. 2 s
0.4 0.6 0.8 1.0 1.2 1.4
Energy E [Ry]
Fig. 102. Nb. Total and partial densities of states from
For Figs. 100, 101 see next page self-consistent energy bands using the α = 2/3 exchange
approximation [77B].
0.7 3 1 1 1
5
0.6
Nb 1 1 3
15 4 15
3
0.5
0.4 2 3
25’ 3 25’
0.3 1 3
4 2 3
0.2 4 4 3 3
12 3 12
2’ 1 1
1 1 1’
0.1
Energy E [Ry]
1 3
5 1’ 3 1
0 25’ EF 25’
− 0.1 3
2 3 2 4
−0.2 24
4 2 1
4 3
−0.3 1 1
1 1 1
1
−0.4 12 1
12
1
−0.5 1
−0.6
−0.7
Γ ∆ H G N D P Λ Γ Σ N P F H
Wavevector k
Fig. 100. Nb. Energy bands from a self-consistent all-electron
calculation, employing density-functional theory and the linear
combination of Gaussian orbitals method [88J1]. See also [77E, 78M,
79L]. Symmetry labels in single group notation.
72
Nb
60
EF
DOS [ states Ry −1atom −1]
48
36
24
12
0
− 0.5 − 0.3 − 0.1 0.1 0.3 0.5 0.7 0.9
Energy E [Ry]
Fig. 101. Nb. Density of states calculated from the band structure shown
in Fig. 100. [88J1]. See also [77E].
3 Nb Nb (100) s1’
2 ∆1 s1
1 total d hν = 26 eV
0 25
2 d − eg
23
21
1
19
18
0
Intensity I
17
3 d − t2g
2
15
1
0
−6 −4 −2 0 2 4 6
Fig. 103. Nb. Partial d-like densities of states calculated

for the bcc phase [00G]. 13
−12 −10 −8 −6 −4 −2 0 = EF
24 1 Initial state energy E i [eV]
Nb
20 Fig. 104. Nb(100). Normal-emission photoelectron
spectra taken at different photon energies hν. Peaks
labeled s1 and s′1 originate from surface resonances at
16 k|| = 0, solid line labeled ∆1 shows the dispersion of the
1
lower ∆1 bulk band [98F2].
12
Energy E [eV]
15
8 1
2’ 25’ Nb (001)
4 12
5 0.00 Γ
25’ EF
0.10
0
2
0.17
−4 1 12 0.26
1 0.39
−8
Γ ∆ H
Intensity I
0.51
Wavevector k
0.58
Fig. 105. Nb. Solid lines: bulk band structure calculated
in [79L]. Filled circles represent experimental data 0.64
derived from spectra shown in Fig. 104 [98F2].
0.68
→
0.81
Fig. 106. Nb(001). Angle-resolved photoelectron
spectra taken at various relative k|| values between Γ 0.91
and X of the surface Brillouin zone showing dispersion 1.00 X
of several surface states (resonances). Photon energy
21.2 eV [94F]. See also [93F]. −6 − 5 − 4 −3 −2 −1 0 = EF 1 2 3
Nb (001) Nb (110)
0.00 Γ
0.11
0.16
0.22
0.27
0.32
Intensity I
0.37
0.42
0.47
Intensity I
0.52
0.56
0.61
0.66
0.71
0.76 −16 −14 −12 −10 − 8 −6 −4 −2 0 = EF
0.80 Initial state energy E i [eV]
0.84
0.88 Fig. 108. Nb(110). Normal-emission photoelectron
0.92
spectrum taken with photons of 21.2 eV [81S2].
1.00 M
−6 − 5 − 4 −3 −2 −1 0 = EF 1 2 3
Initial state energy E i [eV] Nb (110) E i [eV] = 33
Fig. 107. Nb(001). Angle-resolved photoelectron
spectra taken at various relative k|| values between Γ
31
and M of the surface Brillouin zone showing dispersion
of several surface states (resonances). Photon energy
21.2 eV [94F]. See also [94F] for data taken along the
29
M-X direction.
27
Intensity I
25
Nb (100) E i [eV]
32.2
31.2
30.2 23
29.2 21
28.2 19
17
27.2
26.2 15
25.2
24.2 0 = EF 5 10 15
23.2 Energy E [eV]
Intensity I
Fig. 110. Nb(110). Normal-incidence inverse

22.6 photoemission spectra as a function of the incident
21.6
electron energy Ei. The dashed line indicates the position
20.6
of a plasmon peak at fixed photon energy [89P1].
19.6
16.6 ←
15.5 Fig. 109. Nb(100). Normal-incidence inverse
14.3 photoemission spectra as a function of the incident
electron energy Ei. The dashed line indicates the
position of a plasmon peak at fixed photon energy
0 = EF 10 20 [89P1].
Energy E [eV]
Nb (110) Nb (110)
E i [eV]
38
Intensity I
Intensity I
14 22 18
26 30 34
Energy Ei [eV]
Fig. 111. Nb(110). Intensity of the direct transition 3.5
eV above EF in Fig. 110 as a function of incident 28
electron energy [89P1].
22.526.5 28.5 30.5 32.5 34.5 36.5
24.5
Fig. 112. Nb(110). Normal-incidence inverse
photoemission spectra showing photon intensity for
different incident electron energies Ei (given in 0.5 eV
steps from 28 to 38 eV) vs. energy of the emitted
photons [88J2].
25
Nb (110)
25
20
1
15
Energy E [eV]
1
10
5 4 4 12
1 1
Fig. 113. Nb(110). Dispersion of the unoccupied bands
3 above EF as determined (vertical dashes) from the data
EF 25’
0 shown in Fig. 112 [88J2]. Solid lines show calculated
2 bands from [77E]. The calculated Σ1 band between 12
1
and 20 eV above EF was used to determine k⊥ [88J2].
N Σ Γ
Wavevector k
Ref. p. 337] 2.11 Nonmagnetic transition metals (Mo) 205
2.11.8 Mo (Molybdenum) (Z = 42)
Lattice: bcc. a = 3.147 Å [71L]

Work function [95H]:
φ (poly) = 4.6 eV
φ (100) = 4.53 eV
φ (110) = 4.95 eV
φ (111) = 4.55 eV
Typical errors are ± 0.2 eV.
Table 10. Mo. Core-level binding energies in eV

Level n=3 n=4
ns1/2 506.3 63.2
np1/2 410.6 37.6
np3/2 394.0 35.3
nd3/2 231.1 –
nd5/2 227.9 –
Table 11. Mo. Energies (in eV w.r. to EF) of band structure critical
points determined experimentally and from different calculations
[79Z].
Level Experiment Theory

[76C2] [73I] [79Z]
Γ1 – –5.92 –5.67
Γ25' –1.5 –1.49 –1.52
Γ12 – 1.37 1.51
H12 –5.0 –6.24 –5.21
H25' – 4.16 3.21
206 2.11 Nonmagnetic transition metals (Mo) [Ref. p. 337
Figures for 2.11.8
10
2 Mo
4d
10
3d
1
3p 3d
3p
–1
10 3s
4s
4d
10
–2 4s 4p
–3
10
5s
10−4
0 200 400 600 800 1000 1200 1400
Fig. 114. Mo. Atomic subshell photoionization cross sections for photon
2
10
Mo
10
–1
10
–2
10
0 50 100 150 200 250 300 350
Fig. 115. Mo. Atomic 4d-subshell cross section near the Cooper
minimum [85Y].
MNV
Mo 3d 5/2
3d 3/2
1080 1065 1050
Eb [eV]
MNV
Intensity I
3p 3/2 Fig. 116. Mo. Overview XPS

3p 1/2 spectrum taken with unmono-
chromatized MgKα radiation. The
3s
insert shows a blow-up of the
MNV Auger electron spectrum
4p [95M]. For results obtained with
4s monochromatized AlKα radiation
see [95M].
1200 1000 800 600 400 200 EF = 0
Mo 3d 5/2 Mo (110)
227.7
3d 3/2
hν [eV] = 340
Intensity I
320
300
Intensity I
290
3.15
280
270
240 230 220
Binding energy E b [eV] 265
Fig. 117. Mo. XPS spectrum showing the region of the 260
spin-orbit-split 3d core levels taken with unmono-
chromatized MgKα radiation [79W]. See [83W] and 229 228 227 226
[95M] for similar results. Binding energy E b [eV]
Fig. 118. Mo(110). Photoemission from the 3d5/2 core

levels, taken at different photon energies hν in normal
emission with the sample at 100 K [93L]. For ab initio
calculation of the surface-core level shift see [94A].
8
Mo
1.5
6
DOS [states/eV⋅atom]
1.0 s
p 4
Intensity I
d
0.5 EF
2
BG
0 0
−10 −8 −6 −4 −2 0 = EF 2 −10 −8 −6 −4 −2 0 = EF 2
Fig. 119. Mo. Right panel: XPS valence band spectrum left panel [81H2]. See also [80A2] and [83W]. For
taken with monochromatized (0.5 eV) AlKα radiation spectra taken at hν = 84…120 eV, including effect of
from a polycrystalline sample (data points) compared to argon-ion bombardment, see [91K1]. For angle-
a simulated one (solid line and assumed background, integrated data from Mo(100) at 21.2 and 16.8 eV see
BG) employing partial DOS calculations shown in the [77W1].
Mo
Intensity I
0
DOS
Fig. 120. Mo. Top: Experimental bremsstrahlung

resolution 0.7 eV). Bottom: calculated DOS without
0 broadening (dashed) and (solid line) broadened to
simulate experimental and lifetime widths [84S].
0 2 4 6 8 10
1.0
Mo
0.8
0.6
Reflectivity R
0.4
Fig. 121. Mo. Experimental normal-

0.2 incidence reflectivity data obtained
from different experiments [81W1].
For details and tables of "most
recommended" data see [81W1].
0 5 10 15 20 25 30
20
Mo
15
10 ε 2
10
ε2
ε 2 /10
5
Fig. 122. Mo. Experimental ε2 spectra

0 5 10 15 20 25 30 [81W1]. See also caption to Fig. 121.
Mo
EF
DOS
Fig. 124. Mo. Calculated DOS based on a band

structure using the KKR method and first-principles
self-consistent potentials [84S]. See also [79Z].
−6 −4 −2 0 2 4 6
Mo 3 1 1
12
0.8 5 1 1 1 3
3 10
15
0.6 15 4 1 8
3
1 2 3 6
0.4 25’
25’
4
4 3
0.2 2’ 4 3 2
Energy E [Ry]
4 2
Energy E [eV]
1’ 3 3
5
1 1 12
12 1
0 0
EF 3 3 1
1
3 −2
− 0.2 25’ 2 2 25’
4 2 4 4
4
3 −4
2
1 12
− 0.4 1
1 1 1
1 1 −6
12
1 1
−0.6 −8
−10
−0.8
Γ ∆ H G N Σ Γ Λ P D N D P F H
Wavevector k
Fig. 123. Mo. Band structure calculated using the RS-LMTO-ASA
method in a non-relativistic treatment. Energy scale relative to EF [00L].
For bands at higher energies above EF see [79Z]. See also [73I].
2
Mo 5 6 5 6
5 8+
4+5 5
7
6 5
EF 5
7
6 5
7+
8
8+
−2 6
Energy E [eV]
7
5 5
4+5 4+5 5
−4
5
6
6
5
5 6
−6
6+
−8
H P N P Γ N H Γ
Wavevector k
Fig. 125. Mo. Energy bands calculated using a nonorthogonal tight-
binding interpolation scheme including the spin-orbit-interaction [88J3].
Symmetry labels in double group notation.
0.5
Mo
EF
Energy E [Ry]
− 0.5
Fig. 126. Mo. Orthogonal tight-

binding band structure (dots) in
comparison with an ab initio LMTO-
ASA band structure (solid lines)
−1.0 [98H].
Γ ∆ H G N Σ Γ Λ P F H
Wavevector k
3 Mo Mo (100)
2 total d
1
0
2 hν [eV]
d − eg
1 40
Intensity I
0 25
3
2 d − t2g
20
1
0
−6 −4 −2 0 2 4 6
Energy E − E F [eV] 17
Fig. 127. Mo. Partial d-like densities of states calculated

for the bcc phase [00G]. 15
−3 −2 −1 0 = EF
Fig. 128. Mo(100). Normal-emission photoelectron
spectra taken at different photon energies hν [91S1]. For
photon energies up to 48 eV see [93S]. See also [77N] for
earlier work. For spectra taken at hν = 10.2…21.2 eV
within a 10°-cone around normal emission see [76C2].
For influence of hydrogen-adsorption see [91S2].
Mo (001) Mo (001)
hν = 21.22 eV
S EF k II [Å −1]
B
B 0.99
SR SR 0.93
0.86
Intensity I
( A)
0.80
0.74
Intensity I
0.67
(B ) 0.61
0.54
0.41
0.34
−5 −4 −3 −2 −1 0 = EF 0.27
Initial state energy E i [eV] 0.21
Fig. 129. Mo(001). High-resolution normal-emission 0.14
photoelectron spectra for a clean (A) and a hydrogen 0
covered (B) surface, demonstrating sensitivity of
surface state S at Ei = –0.3 eV. B and SR denote bulk −3 −2 −1 0 = EF
emission and surface resonance emission, respectively
[93S]. Fig. 130. Mo(001). Angle-resolved photoemission
spectra taken with !ω = 20 eV at different k|| along the
Σ direction of the surface Brillouin zone [91S1]. See
also [79I] for earlier work.
Mo (001) Mo (001)
θ=
B SR 25° k II / Γ M
SR 0.46
0.41
20°
Intensity I
Intensity I
0.33
15°
0.24
10° 0.14
5° 0.06
SR
B S 0
0°
−5 −4 −3 −2 −1 0 = EF −2 0 = EF 2 4 6
Initial state energy E i [eV] Energy E [eV]
Fig. 131. Mo(001). Angle-resolved photoelectron Fig. 132. Mo(001). Inverse photoemission spectra taken
spectra taken with hν = 21.2 eV at different angles θ at different k|| of the incident electrons along ΓM of the
along the ∆-direction of the surface Brillouin zone surface Brillouin zone at fixed electron energy Ei = 14.3
[93S]. Sample at 52 K. For the meaning of S, SR, B see eV [86D1].
Fig. 129.
Mo (110) Mo (011)
k II [Å −1]
0.67
0.64
0.60
0.54
Intensity I
0.49
0.46
Intensity I
0.44
0.43
0.42
0.41
0.40
−5 −4 −3 −2 −1 0 = EF 0.39
Initial state energy E i [eV] 0.38
0.35
Fig. 133. Mo(110). Normal-emission photoelectron
0.31
spectrum using monochromatized HeI (21.2 eV)
radiation [00K2]. For effects of residual gas exposure 0.27
even in UHV see [00K1]. See also this source for −3 −2 −1 0 = EF
surface Fermi contours. Initial state energy E i [eV]
Fig. 134. Mo(011). Angle-resolved photoelectron

spectra taken with hν = 24 eV at different k|| along the ∆
direction of the surface Brillouin zone [88J3]. For an
experimental surface Fermi contour see [89J].
Mo (112) Mo (112) hν [eV]
hν [eV] 83
28 80
77
26 74
71
24
Intensity I
68
Intensity I
65
62
22 59
56
53
20 50
47
18 44
41
35
16 32
−4 −3 −2 −1 0 = EF −8 −7 −6 −5 −4 −3 −2 −1 0 = EF
Fig. 135. Mo(112). Normal-emission photoelectron Fig. 136. Mo(112). Normal-emission photoelectron
spectra taken for photon energies 16…28 eV [01Y]. spectra taken for photon energies 32…83 eV [00Y].
0
Mo (112)
−0.5
−1.0
−1.5
−2.0
−2.5 T [K]
−3.0 320
Intensity I
−3.5
350
−4.0 Mo (112)
378
−4.5
405
−5.0
15 25 35 45 55 65 75 85 95 430
454
Fig. 137. Mo(112). Experimental band dispersion
observed in normal-emission as a function of photon 476
energy [01Y], see also Figs. 135 and 136. See [01Y] for
−6 −5 −4 −3 −2 −1 0 = EF
a detailed analysis separating bulk and surface sensitive
features.
Fig. 138. Mo(112). Normal-emission valence band
spectra for various temperatures. Photon energy 55 eV
[96W].
θ = 35°
Mo (112)
30°
25°
20°
Intensity I
15°
10°
5°
0°
Fig. 139. Mo(112). Angle-resolved inverse
photoemission spectra taken in the isochromat mode
(hν = 9.5 eV) at different electron incidence angles
_2 θ along the Γ-Y surface Brillouin zone direction [01J].
−1 0 = EF 1 2 3
Energy E [eV]
Ref. p. 337] 2.11 Nonmagnetic transition metals (Tc) 215
2.11.9 Tc (Technetium) (Z = 43)
Lattice: hcp. a = 2.743 Å, c = 4.400 Å, c/a 1.604 [71L]

Work-function:
φ (poly) = (4.88 ± 0.3) eV [95H]
φ (poly) = (5.0 ± 0.3) eV [84C1]
Table 12. Tc. Core-level binding energies in eV

relative to EF [90K1, 95H]. Estimated accuracy is ±
0.2 eV [90K1].
n=3 n=4
ns1/2 544.0 69.9
np1/2 447.6 42.3
np3/2 427.6 39.9
nd3/2 257.5 –
nd5/2 253.9 –
For core-level widths see [90K1] and [92F].
Figures for 2.11.9
2
10
Tc
10
4d
3d
1
3d
3p
–1
10 3s
4s 4p
4d
–2
10
4s
5s
–3 Fig. 140. Tc. Atomic subshell
10
photoionization cross sections for
photon energies between 0 and 1500
10−4 eV [85Y].
0 200 400 600 800 1000 1200 1400
216 2.11 Nonmagnetic transition metals (Tc) [Ref. p.337
Tc
10
–1
10
–2
10
0 50 100 150 200 250 300 350
Fig. 141. Tc. Atomic 4d-subshell cross section near the Cooper
minimum [85Y].
Tc M5
M4
Intensity I
1904 1908 1912 1916 1920 1924

Kinetic energy E k [eV]
Fig. 142. Tc. The M4,5 internal-conversion electron spectrum from

99m
polycrystalline metallic Tc (dotted). The result of the
separation of the M5 line is shown by a continuous line [90K1].
Ref. p. 337] 2.11 Nonmagnetic transition metals (Tc) 217
Tc
1.1
EF
0.9
Energy E [Ry]
0.7
0.5
s p d total
0.3
3 1.5 0 1 0 15 0 30 0 Γ M K Γ A L H A M L K H
DOS Wavevector k
Fig. 143. Tc. Right panel: Band structure calculated self-consistently by means of the full potential linearized APW-
method [88B] and (left panel) resulting s,p,d-like partial densities of states (in states/Ry/atom) as well as total DOS
(states/Ry/unit cell) [88B]. For earlier work see also [77F, 79A, 83C].
Tc
Ne I
He I
Intensity I
Fig. 144. Tc. Angle-integrated photoemission spectra

taken at hν = 21.2 eV (HeI) and hν = 16.8 eV (NeI),
respectively [84C1]. The dashed curve reproduces the
DOS calculated in [79A].
−8 −6 −4 −2 0 = EF
218 2.11 Nonmagnetic transition metals (Ru) [Ref. p. 337
2.11.10 Ru (Ruthenium) (Z = 44)
Lattice: hcp. a = 2.706 Å, c = 4.281 Å, c/a = 1.582 [71L]

Work-function:
φ (poly) = (4.7 ± 0.3) eV [95H]
φ (0001) = (5.4 ± 0.1) eV [81H1]
Table 13. Ru. Core-level binding energies in eV w.r.

to EF [95H]. Typical scatter between different
Level n=3 n=4
ns1/2 586.1 75.0
np1/2 483.5 46.5
np3/2 461.3 43.2
nd3/2 284.1 –
nd5/2 280.0 –
Table 14. Ru. Energies of band structure critical points determined experimentally and theoretically,
given in eV w.r. to EF. Error bars estimated from the experimental data to be about ± 0.2 eV.
Critical Point Experiment Theory

energy level [81H1] [86L2] [75J1] [81H1]
Γ1+ –7.5 –7.3 –8.2 –7.0
Γ4– –5.6 – –6.0 –5.8
Γ6–,1+ –2.4 –2.45 –2.75 –2.6
–2.5 –2.3
–2.3
Γ5+ –1.7 – –2.05 –1.8
–1.75
Γ6+ – –1.2 –1.45 –1.2
–1.3
Γ2+ +16.4 +16.5 – +15.0
Ref. p. 337] 2.11 Nonmagnetic transition metals (Ru) 219
Figures for 2.11.10
10
2 Ru
4d
10
1 3d
3p 3d
–1
10 3s
4d
4p
–2
10 4s
–3
10 5s
10−4
0 200 400 600 800 1000 1200 1400
Fig. 145. Ru. Atomic subshell photoionization cross sections for photon
2
10
Ru
10
–1
10
–2
10
0 50 100 150 200 250 300 350
Fig. 146. Ru. Atomic 4d-subshell cross section near the Cooper
minimum [85Y].
M45 N1 N23
Ru 1102 3d 5/2
M45 N1 V
1052 M45 N23 V
1023
M45 VV 3d 3/2
I
979.2
MNN
1115 1065 1015 965

Intensity I
MNV Eb [eV]
3p 3/2
3p 1/2
Fig. 147. Ru. Overview XPS spectrum
3s taken with unmonochromatized MgKα
radiation [95M]. The insert shows a blow-
up of the MNN Auger electron spectrum
4p
4s [79W]. For data with monochromatized
AlKα radiation see [95M].
1200 1000 800 600 400 200 EF = 0
S2 b S1
Ru Ru (0001)
3d 5/2
280
hν [eV]
3d 3/2 400
Intensity I
Intensity I
4.1
292 282 272

Binding energy E b [eV] 370
Fig. 148. Ru. XPS spectrum showing the region of the
spin-orbit-split 3d core levels taken with unmono-
chromatized MgKα radiation [79W]. See also [95M].
352
280.8 280.4 280.0 279.6 279.2

Fig. 149. Ru(0001). High-resolution study of surface

core level shifts at the 3d5/2 peak performed at three
different photon energies. Energy resolution better than
80 meV. Solid lines indicate decomposition into three
components, related to emission from bulk (b), first
layer atoms (S1) and second layer atoms (S2) [00L].
Ru (1010) Ru
S2
Intensity I
Intensity I
b
S1
clean (1×1)
0
281.5 281.0 280.5 280.0 279.5 279.0 278.5
DOS
Fig. 150. Ru(10 1 0). High-resolution study of the 3d5/2 0

core levels. Photon energy 400 eV, resolution 65 meV.
Solid line indicates emission from bulk atoms, S2 and 0 2 4 6 8 10
S1 result from second and first layer atoms [01B]. For Energy E − E F [eV]
more details and spectra recorded at different photon
energies see [00B1]. Fig. 151. Ru. Top: Experimental bremsstrahlung
resolution 0.7 eV). Bottom: calculated DOS without
simulate experimental and lifetime widths [84S].
1.0
Ru
0.8
0.6
Reflectivity R
0.4
0.2
0 5 10 15 20 25 30
Fig. 152. Ru. Experimental normal-incidence reflectivity data
obtained from different experiments [81W1]. For details and tables of
"most recommended" data see [81W1].
40
Ru
30
10ε 2
20
10
0 5 10 15 20 25 30
Fig. 153. Ru. Experimental ε2 spectra [81W1]. See also caption to Fig.
152.
1.0
EF EF
0.8
0.6
Energy E [Ry]
0.4
0.2
Ru
0
Γ T K T’ M Σ Γ ∆ AM U L K P H S’ L R A S H
Wavevector k
Fig. 154. Ru. Relativistic energy band structure calculated by means of the linear muffin-tin-orbital method [75J1].
See also [78M, 86C].
35 14
Ru EF
Ru
30 12
25 10
DOS [states /( atom ⋅ Ry)]
NOS [electrons / atom]
DOS
20 8
15 6
0
10 4
EF −6 −4 −2 0 2 4 6
Energy E - E F [eV]
5 2
Fig. 156. Ru. Calculated DOS based on a band structure
using the KKR method and first-principles self-
0 0 consistent potentials [84S].
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Energy E [Ry]
Fig. 155. Ru. Density of states calculated from the band
structure shown in Fig. 154 [75J1].
Ru
1.1
EF
0.9
Energy E [Ry]
0.7
0.5
s p d total
0.3
3 1.5 0 1 0 15 0 30 0 Γ M K Γ A L H A M L K H
DOS Wavevector k
Fig. 157. Ru. Right panel: Band structure calculated self-consistently by means of the full potential linearized APW-
method [88B]. Left panel shows corresponding s,p,d-like partial densities of states (in states/Ry/atom) and the total
DOS (states/Ry/unit cell) [88B]. See also [78M, 86C].
2
Ru (001)
15 1 40 65
2
10 35 60
5
Energy E [eV]
5 30 1 55
ss1
2
5 6
2
0 = EF 25 50
6 5
5
6
1 6
ss2
−5 20 45
1
2
1 2
Γ ∆ A Γ ∆ A Γ ∆ A
Wavevector k
Fig. 158. Ru(001). Calculated occupied and empty energy bands along ΓΑ [86L2]. Dots correspond to free-electron-
like bands fitted to experimental critical points marked with squares, dashed lines present photoemission final-state
bands. SS1 and SS2 refer to surface states [86L2].
hν [eV] Ru (001)
24
22 hν [eV]
24
20
22
19
18 21
17
Intensity I
Intensity I
19
16
18
14
12 17
16
14
12
−10 −8 −6 −4 −2 0 = EF −6 −4 −2 0 = EF 2
Fig. 159. Ru(001). Left panel: experimental polarization see [81H1]. Right panel: Theoretical
photoelectron spectra excited by p-polarized light in photoemission spectra corresponding to the parameters
normal emission at different photon energies between of the left panel. Dashed line displays background for
12 and 24 eV. Arrows indicate structure due to final hν = 12 eV [86L2]. For a spectrum taken at hν = 21.2
states [86L2]. For results obtained with mixed eV see also [99B].
Ru (001)
hν [eV]
50
48 hν [eV]
46 50
48
44
46
42 44
Intensity I
42
Intensity I
38
36 38
34 36
32 34
30 32
28
30
26
28
26
−10 −8 −6 −4 −2 0 = EF −6 −4 −2 0 = EF 2
Fig. 160. Ru(001). As figure 159 but for higher photon energies between 26 and 50 eV [86L2].
θ = −55° Ru (001)
Ru (001) −50°
−40°
0 = EF −30°
−20°
−15°
−10°
−5°
−2
0°
Intensity I
5°
−4
10°
15°
20°
−6 30°
40°
50°
−8
Γ‘ A Γ
−10 −5 0 = EF
Wavevector k
Fig. 161. Ru(001). Experimental occupied bands
derived from normal-emission spectra (squares: light Fig. 162. Ru(001). Experimental off-normal
incidence angle α = 20°, circles: α = 75°) compared to photoemission spectra taken at different polar angles θ
calculated bands (solid lines) [86L2]. along ΓK of the surface Brillouin zone. Photon energy
38 eV [86L2].
Ru (001) Ru (001)
S1
B2
B1 S2
Intensity I
Intensity I
0 = EF 2 4 6 8
Energy E [eV] 10 15 20 25 30
Energy E [eV]
Fig. 163. Ru(001). Inverse photoemission spectrum
taken in the isochromate mode at hν = 9.7 eV [87B2]. Fig. 164. Ru(001). Unoccupied electronic states
Labels B and S denote emission of bulk and surface reflected in different electron spectroscopies. Top:
origin, respectively. Very-low-energy electron diffraction (VLEED)
intensity versus energy curve taken near (3° off) normal
incidence. Bottom: Normal-emission photoelectron
spectrum excited by photons of 38 eV, showing intense
secondary-electron emission structure at electron
energies below 20 eV [86L1]. From the original
photoemission spectrum (dashed line) a smooth
background was subtracted.
Ref. p. 337] 2.11 Nonmagnetic transition metals (Rh) 227
2.11.11 Rh (Rhodium) (Z = 45)
Lattice: fcc. a = 3.804 Å [71L].

Work-function:
φ (111) = (5.4 ± 0.1) eV [89G2].
Table 15. Rh. Core-level binding energies in eV w.r.

to EF [95H ]. Typical scatter between different
Level n=3 n=4
ns1/2 628.1 81.4
np1/2 521.3 50.5
np3/2 496.5 47.3
nd3/2 311.9 –
nd5/2 307.2 –
Table 16. Rh. Experimental and theoretical critical point energies (in eV relative to EF) [89G2].
Symmetries in double (single) group notation.
Energy Experiment Theory
level [89G2] [73C] [74S1] [79B1] [81B]
L6+ (L1) –5.6(5) –5.54 –6.0 –5.8 –5.2
X7+ (X3) –5.0(1) –5.36 –5.5 –5.2 –5.0
Γ8+ (Γ25') –3.1 –3.00 –2.8 –2.9
–2.75(10)
Γ7+ –2.8 –2.74 –2.5
L6+ (L3) –3.07 –3.3 –3.1 –3.0
–2.65(10)
L4+, 5+ –2.78 –3.0 –2.7
Γ8+ (Γ12) –0.85(10) –1.09 –1.2 –1.0 –1.0
L6+(L1) 9.0(5) 8.17 8.7 8.7 8.7
Γ7− (Γ2') 16.1(5) 16.4 – 16.4 17.8
Γ6– (Γ15) 20.3 21.1 22.4
20.5(5) –
Γ8– 20.4 23.1
228 2.11 Nonmagnetic transition metals (Rh) [Ref. p. 337
Figures for 2.11.11
2
10
8
6 Rh
4
2
4d
10
8
6
4
1
8
6
4
2 3d
–1 3p
10
8
6
4 3s
2
4p
–2 4d
10 8 4s
6
4
2
–3
10 8
6 Fig. 165. Rh. Atomic subshell
4 photoionization cross sections for
5s photon energies from 0 to 1500 eV
2
–4 [85Y].
10
0 200 400 600 800 1000 1200 1400 1600
50
4
Rh
3
10 9
8
7
6
5
4
3
19
8
7
6
5
4
3
2
Fig. 166. Rh. Atomic 4d-subshell
–1
cross section near the Cooper
10 minimum [85Y].
0 50 100 150 200 250 300 350 400
Rh MNN
M45N1 V
1031
M45N23 V
1001 M45V V
952.1
MNN
1050 1000 950 900
Eb [eV ]
3d5/2
Intensity I
3d3/2
3p3/2
3p1/2
EF
3s
(× 4)
4p
4s
1100 1000 900 800 700 600 500 400 300 200 100 0
Fig. 167. Rh. Overview XPS spectrum taken with unmonochromatized MgKα radiation. The insert shows a blow-up
of the MNN Auger electron spectrum [79W]. For results with monochromated AlKα radiation see [95M].
3d5/2
Rh 307.0
3d3/2
Intensity I
Fig. 168. Rh. XPS spectrum showing the region of the

spin-orbit-split 3d core levels taken with
unmonochromatized MgKα radiation [79W]. For the
4.75 core line asymmetry of data taken with mono-
chromatized AlKα radiation see [74H1]. See also
[95M].
320 318 316 314 312 310 308 306 304 302 300
s
Rh(100) hν = 370 eV Rh b
b
s
Intensity I
(110)
Intensity I
309.0 308.5 308.0 307.5 307.0 306.5 306.0 305.5 305.0
Fig. 169. Rh(100). Photoemission spectrum of the 3d5/2
core level and (solid lines) its decomposition into
emission from bulk (b) and surface (s) atoms [00R]. For (111)
results obtained at different photon energies and
detailed discussions see also [94B, 96Z1, 96Z2, 01K2].
Rh
310 309 308 307 306 305 304
Fig. 170. Rh. High-resolution spectra of the 3d5/2 level

for the (111) surface (bottom) and the (110) surface
(top) taken at photon energies hν = 380 eV (bottom)
and 370 eV (top). Dots are experimental data, solid
Intensity I
DOS
lines show individual bulk (b) and surface (s)

components [94A]. For Rh(110) spectra taken at hν =
397 eV see [96Z2]. For Rh(111) see also [01G].
EF
–10 –8 –6 –4 –2 0 2
Fig. 171. Rh. XPS valence band spectrum (dotted)

taken with monochromatized (0.5 eV) AlKα radiation.
The solid curve is the corresponding density-of-states
curve, calculated within the combined interpolation
scheme [74S1] and smoothed with a Lorentzian
broadening to account for experimental resolution
[74S2]. See also [74H2].
1.0
Pd hν = 80 eV Rh
0.8
70
0.6
Reflectivity R
60
0.4
55
50 0.2
48
0 5 10 15 20 25 30
Fig. 173. Rh. Experimental normal-incidence

reflectivity data obtained from different experiments
46 [81W1]. For details and tables of "most recommended"
data see [81W1].
Intensity I
44
20.0
Rh
17.5
42
15.0
Dielectric constant ε2
12.5
40
10.0
7.5
5.0
2.5
30 eV 0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5

Fig. 174. Rh. Experimental ε2 spectra [81W1]. See also

legend to Fig. 173.
EF
–17.5 –15.0 –12.5 –10.0 –7.5 –5.0 –2.5 0 2.5

Fig. 172. Rh(poly). Spectra of the valence band taken at
various photon energies between 30 and 80 eV [84I].
For similar results measured between 40 and 70 eV
from Rh(111) in an angle-integrated mode see [84H2].
14
Rh
12
10
6
Energy E [eV]
2
EF
0
–2
–4
–6
–8
Γ X W L Γ K X
Wavevector k
Fig. 175. Rh. Band structure calculated by a second principles method

using the combined interpolation scheme [74S1].
5.0
Rh 0.60
4.5
0.55
4.0 0.50
3.5 0.45
0.40
–1
–1
3.0
0.35
2.5
0.30
(× 8)
2.0 0.25
1.5 0.20
0.15
1.0
EF 0.10
0.5
0.05
0 0
–8 –6 –4 –2 0 2 4 6 8 10 12
Energy E – EF [eV]
Fig. 176. Rh. Density-of-states calculated with the combined interpolation

scheme and the band structure of Fig. 175 [74S2].
Rh
DOS
Fig. 177. Rh. DOS calculated from

EF a band structure computed by
means of the RAPW method
[73C].
0.1 0.3 0.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9
Energy E [Ry]
Rh
25.0
4–+5–,6–
4+5,6
8– 6 7 + 8– 7+
22.5
–
6 7 6–
20.0 6
7– 7 6
17.5 7–
6–
15.0 6 6–,7–
6–,7–
6
6+
12.5 7
+
Energy E [eV]
6
6.7
10.0
6+
7.5
5.0 6–
6–
2.5 6
6– 7+
7+ 4++5+ 6+
7 EF 7
0 8+ 7+ 8+ 6 6+ 7+
6 6 Fig. 178. Rh. RAPW band
7+ 6 7+ 4+5 structure. Exchange part of
– 2.5 6,7
8+ 7 8+ 6 6+ muffin-tin potential has been
7+ 7+ calculated using a nonlocal
– 5.0 6 7
6 6+ approach [81B]. Symmetry labels
6+ 6+ 5 6+ 6+
5 5 3+4 5 in double group notation.
– 7.5
Γ ∆ X Σ' K Σ Γ Λ L Q W Z X
Wavevector k
0.7
1 1
Rh 3
3
0.6
1 1
0.5
3
0.4 2
3 3
0.3
0.2
4' 1 4'
0.1
Energy E [Ry]
0
5' 2 1' 2' 5'
2
1
– 0.1 EF 3
2
4 2
2
2 1
3 2 4
– 0.2 1
1 3
12 12 4
1
3 3
– 0.3 5 3
2 1
2 3 3
– 0.4 25' 2'
3
1
25'
1
– 0.5 4 1 Fig. 179. Rh. Band structure from
2' 1
1 1
3 3 local density, all electron, self
1 1
– 0.6 1 1 1 consistent calculations [88T].
1 1
1 1 Symmetry labels in single group
– 0.7
notation.
Wavevector k
48
Rh
44
40
36
32
DOS [states (atom Ry) ]
–1
28
24
20
16
12
8
Fig. 180. Rh. DOS calculated from
4 the band structure shown in Fig.
EF
0 179 [88T].
–0.7 –0.6 –0.5 –0.4 –0.3 –0.2 –0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Energy E [Ry]
1.5
6–
Rh(111)
1.0
0.5 4++5+
EF EF 6+
0
– 0.5
– 1.0 8+
8+
– 1.5
– 2.0
7+ 4++5+
– 2.5 7+
– 3.0 6+
8+
8+
– 3.5
– 4.0
– 4.5
– 5.0 6+
– 5.5
– 6.0
– 6.5
6+
– 7.0
– 7.5 6+
– 8.0
L Λ ΓΓ Λ L
Wavevector k
Fig. 181. Rh(111). Comparison of band mapping results (data points) and theoretical band structures (solid lines)
along ΓL. Left panel: bands calculated within the combined interpolation scheme [74S2]. Right panel: calculation of
[81B]. Experimental data from [89G2].
12 1
42.5 Rh(100)
Rh 1
40.0
3'
15
37.5
3 2'
35.0
1
32.5
25'
30.0
Intensity I
1 3
27.5
1 3
25.0
3
22.5 3'
15
20.0
EF
Energy E [eV]
17.5 1
2'
2' –7 –6 –5 –4 –3 –2 –1 0 1
15.0
12.5 1
Fig. 183. Rh(100). Normal-emission photoelectron
10.0
1
spectrum taken at hν = 130 eV [01K2]. For earlier work
using laboratory line sources see [79B1]. For existence
7.5
and properties of an occupied surface state just below
5.0 EF around the M point of the surface Brillouin zone see
A B C
[90M, 94W].
2.5
2'
EF
0
12
3
3
3 Rh(111)
–2.5 3
25' 1
–5.0 1
–7.5
1
1
Intensity I
–10.0
Γ Λ L
Wavevector k
Fig. 182. Rh. Energy bands calculated [79B1] along
ΓL. Vertical arrows indicate direct transitions excited at
hν = 14 eV, compare Fig. 186. Heavy lines characterize
EF
bands with significant free-electron-like character,
dotted line connects calculated bands via free-electron a
parabola. Open symbols above EF indicate experimental
data obtained from photo-emission and/or secondary
electron emission [89G2].

Intensity I
→
Fig. 185. Rh(111). Normal-emission photoelectron EF
spectra excited with 21.2 eV photons with the sample at
(a) room temperature and (b) at 100 K [89G2]. b
–8 –7 –6 –5 –4 –3 –2 –1 0 1
←
Rh(110) polarization : x Fig. 184. Rh(110). Normal-emission photoelectron
spectra for different polarization of the incident light:
hν = 21.2 eV
(a) E parallel [001], (b) E parallel [1 1 0] and (c) E
parallel [110]. From [81B]. For earlier work see also
[79B1].
16.8 eV
A
Rh(111)
Intensity I
11.8 eV hν = 17.3 eV B,C
EF
16.2
a
polarization : y
hν = 21.2 eV
15.0
16.8 eV 14.0
Intensity I
Intensity I
C B A
11.8 eV
13.0
EF
b 12.0
polarization : z
hν = 21.2 eV
16.8 eV 10.9 eV
Intensity I
EF
11.8 eV –10 –9 –8 –7 –6 –5 –4 –3 –2 –1 0
Fig. 186. Rh(111). Normal-emission photoelectron

EF spectra taken at different photon energies between 10.9
and 17.3 eV [89G2].
c
–8 –7 –6 –5 –4 –3 –2 –1 0 1 2
→ Rh(111) E0 = 40.3 eV
Fig. 188. Rh(111). Angle-resolved secondary electron
emission spectra, with emission angle θ oriented along
the ΓLUX plane [89G2]. Ef referred to EF.
θ = 20°
Rh(111) S2 S3
25°
30°
hν = 25.8 eV
35°
40°
24.8
Intensity I
45°
S2 23.7
S3 50°
S2
22.9
55°
21.8
Intensity I
S3
20.7
19.6
5.0 7.5 10.0 12.5 15.0 17.5 20.0
18.4 Final state energy Ef [eV]
18
Rh(111)
17.3 eV
S1 17
16
S2
EF 15
–10 –9 –8 –7 –6 –5 –4 –3 –2 –1 0
Initial state energy Ei [eV] 14
Fig. 187. Rh(111). As Fig. 186 but at photon energies

13
between 17.3 and 25.8 eV. The labels S1, S2 and S3
indicate structure due to secondary electron emission
[89G2]. 12
→ 11
Fig. 189. Rh(111). Experimental conduction band
points obtained from angle-resolved secondary electron
10
spectra [89G2] compared with calculated bands from
(solid line) [73C] and (dashed) [79B1]. Different
symbols refer to different kinematical conditions for 9
excitation of secondary electron emission. See also
[89G2] for experimental results along different k-space 8
Γ Σ K
directions. Wavevector k
Ref. p. 337] 2.11 Nonmagnetic transition metals (Pd) 239
2.11.12 Pd (Palladium) (Z = 46)
Lattice: fcc. a = 3.891 Å [71L]

Work-function:
φ (poly) = (5.2 ± 0.3) eV [95H]
φ (110) = 5.13 eV [90Y]
φ (111) = (5.6 ± 0.1) eV [95K]
Table 17. Pd. Core-level binding energies in eV

with respect to EF [95H]. Typical scatter between
Level n=3 n=4
ns1/2 671.7 87.6
np1/2 560.0 55.7
np3/2 532.3 50.9
nd3/2 340.5 –
nd5/2 335.2 –
Table 18. Pd. Experimental and calculated critical point energies (in eV w.r. to EF).
Critical Experiment Theory
point [78H] [88S3]* [90Y]* [76C1]
Γ – – –2.8 –2.79
–2.55(15) – –2.5 –2.49
–1.15(10) –1.2 –1.1 –1.17
+21.7(5) +21.8 – +21.65
L –0.4(2) –0.3 – –0.14
–0.1(1) –0.1 – +0.05
+7.7(3) +7.8 – +7.3
– +17.0 – +17.2
X – – +13.3 +12.9; +13.3
– – +22.0 +21.3
* Taken from a figure. For states above EF see also [82J].
240 2.11 Nonmagnetic transition metals (Pd) [Ref. p. 337
Figures for 2.11.12
40
Pd
20
4d
10
8
6
4
2
1
8
6
4
2 3d
3p
–1
10
8
6
4 3s
4p
2
4d
–2
10
–3
4s
6⋅10
0 200 400 600 800 1000 1200 1400 1600
Fig. 190. Pd. Atomic subshell photoionization cross sections for photon
40
30 Pd
20
10 9
8
7
6
5
4
3
19
8
7
6
5
4
3
–1
10
0 50 100 150 200 250 300 350 400
Fig. 191. Pd. Atomic 4d-subshell cross section near the Cooper minimum [85Y].
Pd MNN
M45N1 V M5V V
1011 925.6
MNN
M45N23 V
980
3d5/2
3d1/2
1050 1000 950 900

Eb [eV ]
3p3/2
3p1/2
3s
(× 4)
4p
4s
1000 900 800 700 600 500 400 300 200 100 0
Fig. 192. Pd. Overview XPS spectrum taken with unmonochromatized MgKα radiation. The insert shows a blow-up
of the MNN Auger electron spectrum [79W]. For data taken with monochromatized AlKα radiation see [95M].
Pd 3d5/2
334.9
Pd b
s
3d3/2
(110)
5.25
(100)
350 348 346 344 342 340 338 336 334 332 330
Fig. 193. Pd. XPS spectrum showing the region of the

spin-orbit-split 3d core levels taken with
unmonochromatized MgKα radiation [79W]. For the
line asymmetry of data taken with monochromatized
AlKα radiation see [74H1]. See also [95M].
(111)
b s
338 337 336 335 334 333 332

Fig. 194. Pd. 3d5/2 photoelectron spectra from the

Pd(110), Pd(100), and Pd(111) surfaces measured at a
photon energy of 390 eV. The binding energy of the
bulk (b) and surface (s) emission is indicated [94A]. For
Pd other high resolution results see also [96P2] and [92N]
for Pd(100), and [00S] for Pd(111). For ab initio
calculation of surface core level shifts see [94A]. For
PtxPd1-x(111) alloy surfaces see [02R2].
←
Fig. 195. Pd. XPS valence band spectrum (dotted) taken
DOS
with monochromatized (0.5 eV) AlKα radiation. The

solid curve is the Pd DOS calculated within the
combined interpolation scheme [74S1] and smoothed
with a Lorentzian to account for experimental resolution
[74S2]. See also [74H2]. The agreement between
experimental and calculated data may be improved
EF
considerably by inclusion of corrections for matrix-
element modulation, lifetime of the photohole and
inelastic electron electron scattering, see [76H2].
–10 –8 –6 –4 –2 0 2
Pd
hν = 36 eV
30
(× 20)
28
26
(× 20)
24 hν = 150 eV
120
23 (× 10)
22 100
21.2
70
20
19
50 eV
18
16
14 eV
EF EF
–9 –8 –7 –6 –5 –4 –3 –2 –1 0 1 –9 –8 –7 –6 –5 –4 –3 –2 –1 0 1
Fig. 196. Pd. Valence-band photoemission spectra of polycrystalline film for photon energies 14…36 eV (left panel)
and 50 - 150 eV (right panel) [97K]. For valence band spectra from disordered PdxAu1−x (0 ≤ x ≤ 1) see [98N], for
similar data from random PdxAg1−x alloys see [01A].
Pd
Fig. 197. Pd. Bremsstrahlung-

isochromat spectrum taken at hν =
1487 eV (dots) and calculated
DOS
DOS (solid line, bottom) of
unoccupied states. Correspondence
of structures in the experimental
spectrum and features in the DOS
(solid, middle: broadened to mimic
resolution and lifetime effects) is
indicated [85S]. For data shown on
an expanded scale up to 10 eV and
for results obtained from
disordered PdxAu1−x alloys see
[98N]. For further isochromat
studies and theory see [88S5,
EF 88S6, 91S3].
–10 0 10 20 30 40 50 60 70 80
Energy E [eV]
1.0
Pd
0.9
0.8
0.7
0.6
Reflectivity R
0.5
0.4
0.3
Fig. 198. Pd. Experimental
normal-incidence reflectivity data
0.2 obtained from different experi-
ments [81W1]. For details and
0.1 tables of "most recommended"
data see [81W1]. For a calculation
of the full dielectric matrix and
0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 optical properties see [01K1].
5.0
Pd
4.5
4.0
3.5
3.0
2.5
2.0
ε2
1.5
1.0
–1
ε2⋅10 Fig. 199. Pd. Experimental ε2
0.5 spectra [81W1]. See also legend to
Fig. 198. For theoretical results see
[01K1].
0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0
55
Pd
50 For Fig. 200 see next page
45
40
35
DOS [states (atom Ry) ]
–1
30
25
20
15
10
5 Fig. 201. Pd. Density-of-states

function in the d-band range
EF calculated from the RAPW bands
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 of Fig. 200 [76C1].
Energy E [Ry]
3.1
3.0 Pd
2.9
2.8
2.7
2.6
2.5
2.4
2.3
2.2
2.1
2.0
1.9
1.8
1.7
Energy E [Ry]
1.6
1.5
1.4
1.3
1.2
1.1
1.0
0.9
0.8
0.7
0.6 EF
0.5
0.4
0.3
0.2
0.1
0
Γ ∆ X Z W Q L Λ Γ Σ KU S X
Wavevector k
Fig. 200. Pd. Energy bands calculated by means of the relativistic
augmented-plane-wave method [76C1]. For a self-consistent full-potential
total energy KKR calculation including all relativistic effects see [96B].
14
Pd
12
10
6
Energy E [eV]
2
EF
0
–2
–4
–6
–8
Γ X W L Γ K X
Wavevector k
Fig. 202. Pd. Band structure calculated by a second principles method using
the combined interpolation scheme [74S1].
5.0
Pd 0.60
4.5
0.55
4.0 0.50
3.5 0.45
0.40

–1
–1
3.0
0.35
2.5
0.30
(× 8)
2.0 0.25
0.20
1.5
0.15
1.0
0.10
0.5 0.05
EF
0 0
–8 –6 –4 –2 0 2 4 6 8 10 12
Fig. 203. Pd. Density-of-states calculated with the combined interpolation

scheme and the band structure of Fig. 202 [74S2].
23
Pd 22 Pd(111)
21
20
Λ61
19
18
17
16
DOS
15 Λ61
14
13
12
11
EF 10
Energy E [eV]
9
–6 –5 –4 –3 –2 –1 0 1 2 3 4 5 6
Energy E – EF [eV] 8
7
Fig. 204. Pd. DOS curve calculated with the KKR 6
method in the local-density approximation [84S]. For
5
PdxAg1–x alloys see [01A].
4
3
2
0 1
EF EF
Pd(111) 0
Λ4,53
–0.5 –1
3 Λ61
–2 Λ63
–1.0 –3
Λ4,53
–4
Γ Λ L
–1.5 Wavevector k
1
Fig. 206. Pd(111). Experimental band structure data
obtained above and below EF and compared to
–2.0
calculated bands (solid lines). Symmetry labels are
superscribed with single group notation and subscribed
–2.5 3 with double group notation. The calculated empty bands
(solid) are shifted by an energy dependent value
between 0.4 eV and 1.1 eV towards higher energies
–3.0 (dashed curves) in order to improve agreement with the
L Λ Γ
experimental data points above EF. The dashed empty
Wavevector k
bands were used to determine k⊥ for the occupied bands
Fig. 205. Pd(111). Experimental band structure data [88S3].
along Λ [78H].
25 25
24 Pd(111) 24
23 23
22 22
21 1 21
3
20 20
19 2 19
18 18
17 3 3 17
Energy E [eV]
16 2 16
15 15
14 1 14
13 1 13
12 12
11 11
10 10
9 9
Energy E [eV]
8 8
7 7
6 6
5 0 0.1 0.2 0.3 0.4 0.5 0.6
4 Im kz
3
2
1
EF
0
–1
–2
–3
–4
–5
–6
–7
–8
Γ Λ L
Wavevector k
Fig. 207. Pd(111). Relativistic bulk band structure along ΓL with point-group symmetries Λ6 (solid lines) and Λ4+5
(long-dashed lines). Zero energy at EF. Inclusion of an imaginary potential yields short-dashed bands labelled 1,2,3
and associated parts of Imkz shown in the right-hand-side panel. Symbols below EF indicate some experimental
results [89T].
Wavevector k
X K Σ Γ
EF = 0
Pd(110)
–1
4
–2
3
–3
1
–4
1
–5
–6 Fig. 208. Pd(110). Experimental

band mapping results along ΓKX
–7 collected at different experimental
conditions [90Y]. Solid curves
show calculated bands from
–8
2.25 2.50 2.75 3.00 3.25 3.50 3.75 4.00 4.25 4.50 4.75 5.00 [76C1].
–1
Wavevector k⊥ [Å ]
Pd(110)
hν = 40 eV
38
36
34
32
30
28
26
24
22
Fig. 209. Pd(110). Normal-emission photoelectron
spectra from the (1x1) surface taken at different photon
20
energies with light incident at α = 25° and the
18 eV polarization vector in the (001) mirror plane [00B2].
For data at hν from 24 to 68 eV see also Fig. 210
[90Y]. See also [77L2], [80A1] and [85L] for earlier
EF work. For surface Fermi contours on Pd(100) see
[91E1].
–8 –7 –6 –5 –4 –3 –2 –1 0 1
Pd(110)
hν = 24 eV
26
28
30
32
34
36
Intensity I
38
40
42
44
46
48
52
56
60
68 eV
EF
–7 –6 –5 –4 –3 –2 –1 0 1
Fig. 210. Pd(110). Normal-emission photoelectron spectra from the (1x1)

surface taken at different photon energies. The incident light angle is α =
25°, with the polarization vector in the (1 1 0) mirror plane. Dashed lines
indicate dispersion (or nondispersion) of experimental peaks or shoulders
[90Y].
Pd(111) Pd(111)
hν = 30 eV
Intensity I
28
26
24 EF
23
–14 –12 –10 –8 –6 –4 –2 0 2
22
Fig. 212. Pd(111). Normal-emission photoelectron
spectrum collected at hν = 81 eV [01W].
2.50
21
Pd(111)
2.25
20
19 2.00
18 1.75
17
1.50
16
15
1.25
Intensity I
14
1.00
13
12 0.75
0.50
11 EF
0.25
10
0
– 3.5 – 3.0 – 2.5 – 2.0 – 1.5 – 1.0 – 0.5 0 0.5
9 eV Initial state energy Ei [eV]
EF
Fig. 213. Pd(111). Photoelectron spectra collected in
normal-emission at hν = 16 eV using circularly
–6 –5 –4 –3 –2 –1 0 1 polarized radiation. Solid line: data taken without
Initial state energy Ei [eV] polarization analysis. Dashed, dotted lines: separation in
two partial transition intensities by means of the emitted
Fig. 211. Pd(111). Normal-emission photoelectron electron spin polarization [88S3].
spectra taken at various photon energies hν [78H]. For
earlier work see also [77L2, 79D, 81N, 84H1].
Pd(111) Γ – M' Γ– K
θ = – 6° θ = – 8°
0°
0°
10°
20°
10°
30°
20°
40°
28°
50° 32°
52°
55°
60°
66° 40°
EF EF
–6 –5 –4 –3 –2 –1 0 1 –6 –5 –4 –3 –2 –1 0 1
Γ– M
θ = – 6°
– 4°
– 2°
0°
10°
20°
30°
35°
40° Fig. 214. Pd(111). Angle-dependent photoemission
46° spectra taken at hν = 21.2 eV along (a) the Γ-M′
50° azimuth of the surface Brillouin zone, (b) along Γ-
EF K and (c) along Γ-M [97K]. See [97K] also for data
with hν = 16.85 eV.
–6 –5 –4 –3 –2 –1 0 1
c Initial state energy Ei [eV]
Pd(110) L
S θ = – 41°
– 36°
– 31°
S – 26°
– 21°
– 16°
– 11°
– 6° B
– 1°
B
4°
9°
14°
19°
24°
29°
34°
39°
EF
–2 0 2 4 6 8 10 12 14 16 18 20 22 24 26
Energy E [eV]
Fig. 215. Pd(110). Inverse photoemission spectra are labeled B (bulk), S (surface) and L (low-energy-
recorded in the isochromat mode at hν = 9.6 eV for electron diffraction), respectively. For results taken with
electrons incident at indicated angles θ along the ΓY a grating monochromator and parallel photon energy
surface Brillouin zone azimuth [90J]. Spectral features detection see [88S4].
Pd(110)
θ = 77°
L
61°
B
S 41°
B
B
31°
21°
11°
B
1°
B B
EF
–1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Energy E [eV]
Fig. 216. Pd(110). Inverse photoemission, similar to Fig. 215 but with electrons incident along the ΓX direction of
the surface Brillouin zone [90J].
Pd(110) Pd(111)
5 10 15 20 25 30 35 40 45 Γ
Γ2' Γ15 Γ25'
Energy E [eV]
Fig. 217. Pd(110). Low-energy portion of a normal-
emission photoelectron spectrum taken at hν = 50 eV
showing significant secondary electron emission
structure [90Y]. For detailed earlier investigation of
secondary electron spectra see [83L]. E w.r. to EF.
Wavevector k
L
12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5
Energy E [eV]
Fig. 218. Pd(111). Excited-band signatures observed in
low-energy electron reflectance. Top: sample current Ic
versus energy of normally incident electrons and
corresponding second derivative spectrum Ic". Bottom:
relevant section of the bulk bands [82J]. E w.r. to EF.
Pd(111) Γ– M Γ – M'
θ = 60°
θ = 60°
55°
55°
50° 50°
45° 45°
40°
40°
35°
35°
30° 30°
25°
25°
20°
20°
15° 15°
10° 10°
0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0
Fig. 219. Pd(111). Inverse photoemission showing 84W3]. For an inverse photoemission study of the (100)
isochromats at hν = 9.8 eV for electrons incident at surface see [92W]. For two-photon photoelectron
different polar angles in the ΓLUX plane [87I]. For spectra see [87K1]. See also [89K] for theoretical work
earlier work and model calculations see also [86H, on unoccupied states at Pd(111).
258 2.11 Nonmagnetic transition metals (Hf) [Ref. p. 337
2.11.13 Hf (Hafnium) (Z = 72)

Electronic configuration: (Xe) 4f14 5d2 6s2
Work-function:
φ (poly) = (3.9 ± 0.3) eV [95H]
Table 19. Hf. Core-level binding energies in eV w.r. to EF [95H]. Experimental uncertainty estimated to
be up to 1 eV. See also [95M].
ns1/2 np1/2 np3/2 nd3/2 nd5/2 nf5/2 nf7/2
n=4 538.0 438.2 380.7 220.0 211.5 15.9 14.2

n=5 64.2 38.0 29.9 – – – –
For core-hole lifetime broadenings see [92F]
Figures for 2.11.13

20
10
Hf
8
6
4
18
6
4
2 4d
–1 4f
10 4p
8
6
4
3d
4s
2
–2
5p
10
8
6
5s
4
5d
2
–3
10
8
6
–4 6s
4⋅10
0 200 400 600 800 1000 1200 1400 1600
Fig. 220. Hf. Atomic subshell photoionization cross sections for photon
Ref. p. 337] 2.11 Nonmagnetic transition metals (Hf) 259
Hf 4f
4d5/2
4d3/2
4p3/2
4p1/2
4s
NNN
Ni
5p
5s
1200 1100 1000 900 800 700 600 500 400 300 200 100 0
Fig. 221. Hf. Overview XPS spectrum taken with unmonochromatized MgKα radiation [95M]. See also [95M] for
data taken with monochromatized AlKα radiation.
4f7/2 1.50
Hf 14.3 ev
4f5/2 Hf
16.0 eV
1.25

1.00
–1
s
p
d
0.75
0.50
0.25
EF
0
25 23 21 19 17 15 13 11 9 7 5 –10 –8 –6 –4 –2 0 2
Binding energy Eb [eV] Initial state energy Ei [eV]
Fig. 222. Hf. XPS data showing region of the spin-orbit-
split 4f core levels taken with unmonochromatized
MgKα radiation [95M]. For data recorded with
monochromatized AlKα radiation see [79S] and [95M].
For surface core level shift in polycrystalline Hf see [84N].
Hf hν = 22.5 eV
20.4
BG EF
18.7
–10 –8 –6 –4 –2 0 2
15.7 Initial state energy Ei [eV]
Fig. 223. Hf. Bottom: XPS valence band spectrum

taken with monochromatized (0.6 eV) AlKα radiation
14.5
from polycrystalline sample (data points) compared to a
simulated one (solid line and assumed background, BG)
employing partial DOS calculations shown in the upper
12.7 panel [81H2].
11.1 eV
←
Fig. 224. Hf. Bremsstrahlung isochromat spectra taken
EF at different photon energies hν from polycrystalline
sample [92P].
–2 0 2 4 6 8 10
Energy E [eV]
1.0
Hf
0.9
0.8
0.7
0.6
Reflectivity R
0.5
0.4
0.3
0.2 Fig. 225. Hf. Experimental

obtained from different
0.1
experiments [81W1]. For details
and tables of "most recommended"
data see [81W1].
0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0
10
Hf
9
8
10 ε2
7
4
ε2
E II c
3 E⊥c
2
Fig. 226. Hf. Experimental ε2
1 spectra [81W1]. Dashed line E c,
–1
ε2⋅10
dotted line E ⊥ c. See also caption
to Fig. 225.
0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0
1.20
1.15 Hf
1.10
1.05
1.00
0.95
0.90
0.85
0..80
0.75
0.70
Energy E [Ry]
0.65 EF
0.60
0.55
0.50
0.45
0.40
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0
Γ T K T' M Σ Γ ∆ A,M U L,K P H S' L R A S H
Wavevector k
Fig. 227. Hf. Relativistic band structure based on the linear muffin-tin-orbital method [75J1].
30.0 12
Hf
27.5 11
25.0 10
22.5 9
20.0 8
DOS [states (Ry atom) ]
NOS [electrons atom ]

–1
–1
17.5 7
15.0 6
12.5 5
10.0 4
7.5 3
5.0 2
2.5 1
EF
0 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2
Energy E [Ry]
Fig. 228. Hf. Density-of-states calculated from the band structure shown in
Fig. 227 [75J1].
264 2.11 Nonmagnetic transition metals (Ta) [Ref. p. 337
2.11.14 Ta (Tantalum) (Z = 73)
Lattice: bcc. a = 3.303 Å [71L]

Work-function:
φ (100) = (4.15 ± 0.3) eV [95H]
φ (100) = 4.1 eV [90P]
φ (110) = (4.8 ± 0.3) eV [95H]
φ (111) = (4.0 ± 0.3) eV [95H]
Table 20. Ta. Core-level binding energies in eV w.r. to EF [95H]. Experimental errors estimated to be
±0.5 eV. See also [95M].
ns1/2 np1/2 np3/2 nd3/2 nd5/2 nf5/2 nf7/2
n=4 563.4 463.4 400.9 237.9 226.4 23.5 21.6
n=5 69.7 42.2 32.7 – – – –
Figures for 2.11.14

20
10
Ta
8
6
4
4f
2
18
6
4
2 4d
–1 4f
10 4p
8
6
4
4s
2
5p
–2
10
8
6 5s
4 5d
2
–3
10
8
6
–4
6s
4⋅10
0 200 400 600 800 1000 1200 1400 1600
Fig. 229. Ta. Atomic subshell photoionization cross sections for photon
Ref. p. 337] 2.11 Nonmagnetic transition metals (Ta) 265
20
Ta
10 9
8
7
6
5
4
3
19
8
7
6
5
4
3
–1
10 9
8
7
6
5
4
3
–2
10
0 50 100 150 200 250 300 350 400
Fig. 230. Ta. Atomic 5d-subshell cross section near the Cooper minimum [85Y].
4f7/2 S1 21.65 eV
Ta 21.9 ev Ta(100)
4f5/2
23.8 eV
S2
140 meV
B
Intensity I
Intensity I
740 meV
5p3/2
35 33 31 29 27 25 23 21 19 17 15 23.0 22.6 22.2 21.8 21.4

Binding energy Eb [eV] Binding energy Eb [eV]
Fig. 232. Ta. XPS spectrum showing the region of the Fig. 233. Ta(100). High-resolution photoemission
spin-orbit-split 4f core levels taken with unmono- spectrum of the 4f7/2 core level and its decomposition
chromatized MgKα radiation [95M].
into bulk (B) and surface (S1, S2) components [85G].
Photon energy hν = 70 eV. See also [88S7] and [96R].
4f
Ta
NNN
4d5/2
4d3/2
4p3/2
Intensity I
4p1/2
4s
5p
5s
1200 1100 1000 900 800 700 600 500 400 300 200 100 0
Fig. 231. Ta. Overview XPS spectrum taken with unmonochromatized MgKα radiation [95M]. For results obtained
with monochromatized AlKα radiation see [95M].
–720 b
Ta(100) Ta(110)
–715
Core level shift ∆Eb [meV]
–710
–705
–700
50 100 150 200 250 300 22.5 22.4 22.3 22.2 22.1 22.0 21.9 21.8 21.7 21.6 21.5 21.4 21.3
Temperature T [K] Binding energy Eb [eV]
Fig. 234. Ta(100). Experimental surface core level shift Fig. 235. Ta(110). Photoemission spectrum of the 4f7/2
(energy distance between bulk and surface component
core level showing the contributions from bulk (b) and
of the 4f7/2 core level) in its dependence on sample
surface (s) atoms [97S]. Photon energy hν = 120 eV. Eb
temperature [96R].
w.r. to EF. See also [85G] and [88S7].
200
Ta(111)
180
160
140
120
100
80
60
40
20
25.0 24.5 24.0 23.5 23.0 22.5 22.0 21.5 21.0 20.5
Fig. 236. Ta(111). High-resolution photoemission from the 4f doublet. Each

spin-orbit component is decomposed into (starting from lowest binding
energy) a bulk, a sub-surface and a surface line [84W2]. The background used
for decomposition is shown as a dotted line and has a general parabolic shape.
Ta hν = 25.0 eV
22.5
20.4
18.7
15.7
Intensity I
14.5
12.7
11.1 eV
Fig. 237. Ta. Bremsstrahlung isochromat spectra taken

EF
at different photon energies hν from polycrystalline
sample [92P].
–2 0 2 4 6 8 10
Energy E [eV]
1.0
Ta
0.9
0.8
0.7
0.6
Reflectivity R
0.5
0.4
0.3
Fig. 238. Ta. Experimental
0.2 normal-incidence reflectivity data
obtained from different experi-
0.1 ments [81W1]. For details and
tables of "most recommended"
data see [81W1].
0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0
9
Ta
8
6
–1
4 ε2 ⋅ 10
3
ε2
2
scale change
1 Fig. 239. Ta. Experimental ε2
spectra [81W1]. See also legend to
8
Fig. 238.
0 2 4 6 10 15 20 25 30 35 40 45 50
For Figs. 240, 241 see next

pages
Ta(100)
Fig. 242. Ta(100). Normal-

emission photoelectron spectrum
taken at hν = 30 eV. Light-
incidence angle α = 60°, with
linear-polarization vector A
oriented in the mirror-plane along
the ΓM direction of the surface
Brillouin zone [90P]. Some data
points are reproduced to indicate
statistical accuracy. For surface
electronic properties of Ta(110)
see [90K2] and [91K2].
30.0 27.5 25.0 22.5 20.0 17.5 15.0 12.5 10.0 7.5 5.0 2.5 0 –2.5
1.5
Ta
1.4
3 3 1
15
1.3 4 3 15
1
1 3 1 1
1
25' 2 25'
1.2
3
1
1.1 3 2 2 3
4 4 3
12
1.0 4 3 1
1
2' 1
1
1
0.9 1
1' 1'
5
Energy E [Ry]
0.8
25' 3
EF 1 3 3 1
0.7
2
2 3 4 4
2 4 2
0.6 4
4
0.5 1 1 3
1
1 12
1
0.4 1
12
1
0.3
1
0.2
1
0.1
0
Γ ∆ H G N Σ Γ Λ P N P F H
Wavevector k
Fig. 240. Ta. Nonrelativistic band structure [77B].
12
22 Ta
11
20
total 10
18
9
16
DOS [states (Ry atom spin) ]
–1

14
–1
7
12
6
10
5
8
4
6 3
4 2
2 EF
1
0 0
16
d – Γ12
14
–1
12
10
8
6
4
2
0
14
d – Γ25'
12
–1
10
8
6
4
2
0
4
–1
3 p
2
1
0
3 Fig. 241. Ta. Total (top) and partial
2 s
densities-of-states calculated from
1 the bandstructure reproduced in
0 Fig. 240 [77B].
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4
Energy E [Ry]
Ta(100)
kII
Γ [1]
kII
Γ [1]
Γ [0]
center M
odd
–6 –5 –4 –3 –2 –1 0 1 –6 –5 –4 –3 –2 –1 0 1
Fig. 243. Ta(100). Angle-resolved photoelectron in the mirror plane of collection or ((b), right panel)
spectra taken at various polar angles along the Σ (ΓM) perpendicular to the mirror plane of collection, thus
direction of the surface Brillouin zone. Photon energy exciting only even (a) or odd (b) states, respectively
hν = 40 eV. The polarization vector is ((a), left panel) [90P].
Ta(100)
kII kII
Γ [1] Γ [1]
X X
Γ [0] Γ [0]
center center
–6 –5 –4 –3 –2 –1 0 1 – 3.0 – 2.5 – 2.0 –1.5 –1.0 – 0.5 0 0.5 1.0

Fig. 244. Ta(100). Angle-resolved photoelectron spectra taken at various polar angles along the ∆ (ΓX) direction of
the surface Brillouin zone. Ei w.r. to EF. For details see legend to Fig. 243 [90P].
Ta(100) hν = 20 eV
hν = 15 eV
EF
–2 –1 0 1 2 3 4 5 6 7 8 9
Energy E [eV]
Fig. 245. Ta(100). Experimental isochromat spectra
recorded at normal electron incidence and photon
energies hν = 15 and 20 eV [89A]. For angle-of-
incidence dependent spectra recorded at hν = 9.7 eV see
[87B3].
Ref. p. 337] 2.11 Nonmagnetic transition metals (W) 275
2.11.15 W (Tungsten) (Z = 74)
Lattice: bcc. a = 3.165 Å [71L].

φ (poly) = 4.6 eV
φ (100) = 4.63 eV
φ (110) = 5.25 eV
φ (111) = 4.47 eV
Errors estimated to be ± 0.3 eV.
Table 21. W. Core-level binding energies in eV w.r. to EF [95H ]. Experimental scatter between different
sources ± 0.5 eV. See also [95M].
ns1/2 np1/2 np3/2 nd3/2 nd5/2 nf5/2 nf7/2
n=4 594.1 490.4 432.7 256.0 243.4 33.6 31.5
n=5 75.6 45.3 36.8 – – – –
Table 22. W. Comparison of theoretical and experimental energies at high-symmetry points of the bulk
Brillouin zone [98F1]. All energies in eV relative to EF.
Critical Calculation Experiments
point [74C1, 78W2] [84B1]
Γ8+ –1.17 –1.53 –1.32(10) a) ; ≈ – 1.3 b)
Γ7+ –0.61 –1.01 –0.75(5) a); ≈ – 0.4 b)
Γ8+ 1.99 2.15 2.6(2) c)
Γ 14.4 14.9 15.3(5) a); 14.6 (6) b); ≈ 15 d)
Γ 30.2 – 29.7(17) c)
N5+ –3.35 –3.66 –3.40(5) a); –3.5 e)
N5+ 1.96 1.98 2.2(2) c)
N5+ 2.89 2.94 ≥ 3.2 c)
N5+ 5.90 5.88 6.3(5) d)
N5+ 10.7 9.97
10.8(5) d)
N5– 11.1 11.7
N 26.1; 26.9 – 26.5 e)
H8+ –6.1 –5.9 –5.7 b)
H8– 9.0 9.2 9.3 b)
a) Photoemission [98F1]; b) Photoemission [76S]; c) Inverse Photoemission [93D]; d) Photoemission [78W2];
e) Photoemission [82B3].
276 2.11 Nonmagnetic transition metals (W) [Ref. p. 337
Figures for2.11.15
40
20 W
10
8
6
4
4f
2
18
6
4
2
4d
–1
4f
10 4p
8
6
4
4s
2
5p
–2
10
8
6
5d
5s
4
2 Fig. 246. W. Atomic subshell

–3 photoionization cross sections for
10
8 photon energies from 0 to 1500 eV
6
–4
6s [85Y].
4⋅10
0 200 400 600 800 1000 1200 1400 1600
40
30 W
20
10 9
8
7
6
5
4
3
2
19
8
7
6
5
4
3
–1
10 9
8
7
6
5
4
3
2 Fig. 247. W. Calculated atomic

5d-subshell cross section near the
–2
10 Cooper minimum [85Y].
0 50 100 150 200 250 300 350 400
W
4f
NNN
4d5/2
4d3/2
4p3/2
4p1/2
4s
5s
1200 1100 1000 900 800 700 600 500 400 300 200 100 0
Fig. 248. W. Overview XPS spectrum. Data taken with unmonochromatized MgKα radiation [95M]. For data
obtained with monochromatized AlKα see also [95M].
W(110) 4f7/2
5p3/2
4f5/2
Fig. 249. W(110). Wide scan

encompassing the 5p3/2 and 4f
region. High resolution data (∆E =
83 meV) taken with 70 eV photons
[90R]. The spin-orbit-split 4f5/2
and 4f7/2 levels are each split
additionally due to appearance of
the bulk component and a surface-
shifted line, see also Fig. 250.
25 26 27 28 29 30 31 32 33 34 35
Kinetic energy Ek [eV]
S
W(110) W(100)
B
32.00 31.75 31.50 31.25 31.00 30.75 30.50 30.25 32.00 31.50 31.00 30.50 30.00
Binding energy Eb [eV] Binding energy Eb [eV]
Fig. 250. W(110). Analysis of the 4f7/2 photoemission Fig. 251. W(100). High-resolution photoemission from
the 4f7/2 core level, indicating decomposition in (from
spectrum. The data, taken with 70 eV photons, are fitted
with a linear background and two independent lines left to right) a bulk, subsurface and surface line [84W2].
representing the surface (right) and bulk (left) Background used for decomposition is shown as a
contributions [90R]. For effects of sample temperature dotted line and has a general parabolic shape.
see [89P2], for intensity variation with emission angle
see [87J]. Holographic images from surface and bulk
atoms are reported in [99L].
B
W(111) W(100)
F = 45°
40°
32.00 31.50 31.00 30.50 30.00
Fig. 252. W(111). Energy distribution curve of the 4f7/2
photoemission spectrum showing bulk (left) and surface 35°
(right) contributions [88W]. See also [84W2]. For the
thermal shift in the binding energy of the bulk 4f7/2
component see [97T].
30°
Intensity I
25°
20°
15°
10°
5°
Fig. 253. W(100). XPS valence band spectra recorded
with monochromatized AlKα radiation at fixed polar
angle θ = 63° but different azimuth angles Φ [80H]. For
effect of temperature variation on XPS spectra from 0° [102]
W(100) and W(110) see [86W1]. EF
–10 – 9 – 8 – 7 – 6 – 5 – 4 – 3 – 2 –1 0 1
1.0
W
0.9
0.8
0.7
0.6
Reflectivity R
0.5
0.4
0.3
0.2 Fig. 254. W. Experimental

[81W1] obtained from different
0.1
experiments. For details and tables
of the "most recommended" data
see [81W1].
0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0
50
W
45
10 ε2
40
35
30
25
20
ε2
15
10 Fig. 255. W. Experimental ε2

results [81W1] obtained from
5 different experiments. For details
and tables of the "most
recommended" data see [81W1].
0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0
4.4 48
W 46
4.2
44
4.0
42
3.8 40
38
3.6
36
3.4 34
3.2 32
30
3.0
28
2.8 26
24
2.6
22
2.4
20
Energy E [eV]
Energy E [Ry]
2.2 18
16
2.0
14
1.8
12
1.6 10
8
1.4
Evac 6
Evac
Evac
1.2 4
2
1.0
EF
0
0.8
–2
0.6 –4
–6
0.4
–8
0.2
–10
〈100〉 〈110〉 〈111〉
0 –12
Wavevector k
Fig. 256. W. Energy bands along high-symmetry the Fermi level at EF = 0 eV. A prominent feature is the
directions of the bulk Brillouin zone [78W2] as band gap (shaded) which extends throughout the
calculated by a relativistic augmented-plane-wave Brillouin zone, except for the region along the PH line.
method [74C1]. The work functions of each low-index For the calculated density-of-states see [74C1]. For an
face are indicated by the vacuum level Evac relative to approach using an interpolation scheme see also [88S1].
15
1
14 W 1 1 1
4
3
1
13 1
4'
1 3 1
12 3 4 4
5 4'
3
11 1
10 1
1 1
1
9 1
15
15
8 1
4 4
7
3 1 1
6
3
25' 2 25'
5 1
4 1
Energy E [eV]
4 3 3 2 3
4
3 3
12 4 12 1
3 1 3 1
2 2'
1' 1 1'
1
EF 1
0 5 4
–1 3 1
25' 25'
–2 3
3
2 4
2
–3 2 3
4 4
–4 2
1
–5 1 1
1 1
–6 12
1 12
1
–7 1
–8
–9 1 1
–10
Γ ∆ H G N Σ Γ Λ P D NP F H
Wavevector k
Fig. 257. W. Result of a self-consistent semirelativistic pseudopotential calculation of energy bands along high-
symmetry directions of the bulk Brillouin zone [83B1]. Fermi level at zero of energy scale.
W
total s × 50 p × 10 d f × 100
Q = 6.000 Q = 0.254 Q = 0.842 Q = 4.828 Q = 0.075
DOS
–10 –5 0 5 –10 –5 0 5 –10 –5 0 5–10 –5 0 5 –10 –5 0 5

Fig. 258. W. Total and partial (s,p,d,f) densities of states calculated from the semirelativistic energy bands shown in
Fig. 257. Q is the integrated charge density up to EF [83B1].
15
14 W 6
4
6 6
6
13 6 8
12 7 6+
6
5– 4
11 7
6
10 5+
9 8–
6
8
7 6
6–
6 5+
7+
5 8+
6
4
Energy E [eV]
6
8
5+ 4
3 +
8 5 +
4 6
2 7
1 5–
7 EF 6 6
0
+ 6
7
–1
8+
–2 4
7 8
–3 5+
4 7 6
6
–4
6 4
–5 6
–6 5+
8+ 6
–7 6
–8
–9
6+
–10
Γ ∆ H G N Σ Γ Λ P D NP F H
Wavevector k
Fig. 259. W. Result of a self-consistent relativistic pseudopotential calculation of the energy bands [84B1]. See also
[84J] and [85W2]. – Symmetry labels in double group notation.
1.0
1 13
0.9
W
3 1 12
5 3
1
0.8 11
10
0.7 1 3 1
9
0.6 15 2 3 8
3 15
0.5 1 1
25'
7
25' 4
6
0.4 1
3 5
0.3 1 4
2 3
4 3 4
12 4 3 3 3
0.2
Energy E [eV]
Energy E [Ry]
1 1
12 2
2' 1
5 1
0.1 1
1 1
EF 1' 1'
0 0
3
–1
–0.1 3
1 –2
25' 25'
–0.2 –3
2 4 3
2
–0.3 4 –4
4 4
2 2 3
–5
–0.4
1 –6
–0.5 1 1 12
12 –7
1 1
1
–0.6 –8
1
–9
–0.7 1 1
– 10
–0.8
Wavevector k
Fig. 260. W. Energy bands calculated using a first-principles, self-consistent real-space linear muffin-tin orbital
method in the atomic sphere approximation [00L]. Symmetry labels in single group notation.
12 12
W
10 10
8 8
6 6
1
4 4 1,6
2',7
Energy E [eV]
Energy E [eV]
2'
2 2 5,7
2,7
5,6
EF 5 EF
0 0
–2 –2
2,7
–4 –4
–6 1 2 –6
1,6
–8 –8
–10 –10
Γ ∆ H Γ ∆ H
a Wavevector k b Wavevector k
Fig. 261. W. Band structure along the [001] axis, the ΓH direction, for (a) non-relativistic calculation and (b) fully
relativistic calculation [91C]. Symmetry labels in (a) and first label in (b) indicate single-group representations to
which the bands belong in the absence of spin-orbit coupling. Second label in (b) indicates corresponding double-
group representations.
8 8
W
3,5
6 3 6
4 4
4,5
4 4,5
2 1
2
1 1,5
EF EF 3,5 1,5
Energy E [eV]
Energy E [eV]
0 0
1,5
–2 –2
2
2,5
–4 –4
1
–6 –6 1,5
–8 –8
–10 –10
Γ Σ N Γ Σ N
a Wavevector k b Wavevector k
Fig. 262. W. Band structure along the [110] axis, the ΓN direction, for (a) non-relativistic calculation and (b) fully
relativistic calculation [91C]. Symmetry labelling as defined in Fig. 261.
10 W(110) 1
3
6
4
4
2
1
Energy E [eV]
EF
0 1
–2
–4 2
Fig. 263. W(110). Nonrelativistic

–6 band structure calculated along the
1 ΓN line and the corresponding
projected band structure in the
–8
(001) mirror plane [00T2]. Verti-
cally and horizontally hatched
–10 areas denote even and odd bands,
respectively.
Γ Σ NΓ ∆ N
Wavevector k
4
W(110)
3
+
8
2
1
Energy E [eV]
EF
0 Fig. 264. W(110). Experimentally determined energy
+
7 bands along the ΓN line of the bulk Brillouin zone.
+
–1 8 Occupied bands below EF from photoemission [98F1],
empty bands above EF from inverse photoemission
–2 [93D]. The full curves correspond to the relativistic
calculation of [74C1]. The diamonds at EF are from de
–3 Haas-van Alphen data. Symmetry labels in double
group notation.
–4
N Σ Γ
Wavevector k
←
W(001) Fig. 265. W(001). Normal-emission photoelectron
spectra taken at different photon energies hν between
10 and 22 eV. Polarized Synchrotron radiation was
normally incident on the (001) face, i.e. s-polarization
[76S]. See also [78A]. For earlier work on W(100),
hν =
W(110) and W(111) at hν = 8…12 eV see [73F, 74C2].
22 eV
Normal-emission photoelectron spectra from W(111) at
hν = 13 - 30 eV are reported in [82C]. For excitation of
spin-polarized photoelectrons see [81F, 81K].
21
20
W(100)
19
hν =
13 eV
18
15
18
17
21
16
25
29
15
33
14
13 35 eV
12 –5 0 5 10 15 20 25 30 35
Kinetic energy Ek [eV]
11 Fig. 266. W(100). Normal-exit photoemission spectra

measured with various photon energies. P-polarized
10 eV EF light was incident at α = 45°. Arrows indicate peaks
interpreted as surface resonances [78W1]. See also
–20 –16 –12 –8 –4 0
[77W2]. For surface resonances and surface Fermi
Initial state energy Ei [eV] contours see [80C, 81C, 90S, 91E2].
W(100)
Ei = 140 eV
80
50
Fig. 267. W(100). Normal-
40 emission secondary electron
30 spectra taken at different electron
incidence energies Ei. All spectra
20 eV are referred to the zero energy E at
Evac
the vacuum level [81S1]. For
earlier work see [78W2].
0 2 4 6 8 10 12 14 16 18 20
Energy E [eV]
W(100)
Fig. 268. W(100). (a) Normal-emission experimental

secondary electron spectrum after subtraction of a
smooth "background cascade" spectrum [81S1]. (b)
Model calculation based on the "inverse LEED"
Evac formulation which takes the details of the band structure
as well as absorptive and surface effects into account
[81S1]. (c) Fine structure obtained in the experimental
c
electron reflection coefficient [81S1].
0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0
Energy E [eV]
W(001) B
Ei = 18.3 eV
kII /ΓM
Ι 0.87
0.73
16.3
0.57
0.35
14.3
0.14
12.3 eV
EF 0 EF
–2 –1 0 1 2 3 4 5 6 7 8 –2 –1 0 1 2 3 4 5 6
Fig. 269. W(001). Left: Normal-incidence inverse label emission from surface (S), bulk (B) and image
photoemission spectra taken at different energy Ei of potential (I) states. Right: Angular dependence for
the incident electron. Each spectrum corresponds to the electrons incident at Ei = 14.3 eV along the [110] bulk
energy distribution of the emitted photons at fixed Ei , azimuth [86D1]. See also [87K2], [92C], and [94L].
with high photon energies towards the left. S, B, and I
W(110)
C
SR
hν = 27.3 eV
hν = 19.2 eV
26.8
18.8
A 26.3
18.3
17.8 25.8
D
17.3 25.2
16.8 24.8
Intensity I
Intensity I
16.3 24.3
15.8 23.8
15.3 23.2
14.8 22.8
D
A
14.3 21.8
13.8 21.0
12.8 20.8
SR
11.8 eV 19.8 eV
EF EF
– 4.0 – 3.5 – 3.0 – 2.5 – 2.0 –1.5 –1.0 –0.5 0 0.5 – 4.0 – 3.5 – 3.0 – 2.5 – 2.0 –1.5 –1.0 –0.5 0 0.5
Fig. 270. W(110). Normal-emission photoelectron peak amplitude [98F1] and shifted vertically against
spectra taken at different photon energies hν between each other. The feature labeled SR represents emission
11.8 and 19.2 eV (left) and between 19.8 and 27.3 eV from a surface resonance, see also [87G, 89G3].
(right). All spectra are normalized to equal maximum
W(110) W(110)
1.0
0.9
C
0.8
0.7
0.6
kII / k(H)
D
0.5
0.4
A
0.3
0.2
0.1
EF 0
13 14 15 16 17 18 19 –8 –7 –6 – 5 – 4 – 3 – 2 –1 0
Photon energy hν [eV] Initial state energy Ei [eV]
Fig. 271. W(110). Relative variation of peak amplitudes Fig. 274. W(110). Angle resolved photoelectron spectra
of several dispersing features labeled A, C, and D in taken at hν = 21.2 eV along the NΓH azimuth of the
Fig. 270 with photon energy hν [98F1]. bulk Brillouin zone. The parameter on the right gives
the approximate position of k|| (the wavevector parallel
to the surface) in the surface Brillouin zone along the Γ-
H symmetry line, where k||/k(H) refers to the ratio of k||
relative to its value at the H zone boundary [92H].
W(110)
(× 3)
6s,p 5d
EF
–11 –10 –9 –8 –7 –6 –5 –4 –3 –2 –1 0 1
Fig. 273. W(110). Normal-emission photoelectron spectrum taken with hν =

62.5 eV [01R]. For data taken at hν = 40.8 eV see [01S].
W(110)
Intensity I
Intensity I
EF EF
–6 –5 –4 –3 –2 –1 0 1 –6 –5 –4 –3 –2 –1 0 1
Intensity I
Intensity I
EF EF
–6 –5 –4 –3 –2 –1 0 1 –6 –5 –4 –3 –2 –1 0 1
c Initial state energy Ei [eV] d Initial state energy Ei [eV]
Fig. 272. W(110). Normal-emission photoelectron spectra taken at !ω = 21.2 eV with different light polarizations:
Light incidence in (110) plane p-polarized (panel (a)) or s-polarized (b), and incident in (100) plane with p-
polarization (c) and s-polarization (d), resp. [02B].
Σ4
W(110) W(110)
Σ1
hν = 30 eV
Σ1
Ι 28
25
EF
–2 –1 0 1 2 3 4 5 6
22
Energy E [eV]
Fig. 275. W(110). Normal-incidence inverse-
photoemission spectrum taken at fixed electron energy
20
Ei = 14.5 eV showing emission labeled Σ1 , Σ4 from
three bulk bands (compare Fig. 262) and an image
potential state (label I) [93D].
17
15 eV
EF
–1 0 1 2 3 4 5
Energy E [eV]
Fig. 276. W(110). Normal-incidence inverse
photoemission spectra taken in the isochromat mode for
different photon energies hν between 15 and 30 eV
(crosses) compared to photocurrent calculations (full
curves) based on the one-step model of inverse
photoemission [91C]. See also [94S].
Ref. p. 337] 2.11 Nonmagnetic transition metals (Re) 295
2.11.16 Re (Rhenium) (Z = 75)

Work-function:
φ (poly) = (4.7 ± 0.3) eV [95H]
Table 23. Re. Core-level binding energies (in eV relative to EF) [95H, 95M]. Estimated error ± 0.5 eV.
ns1/2 np1/2 np3/2 nd3/2 nd5/2 nf5/2 nf7/2
n=4 625.4 518.7 446.8 273.9 260.5 42.7 40.3

n=5 99 45 35 – – – –
Figures for 2.11.16
40
20 Re
10
8
6
4
4f
2
18
6
4
2 4d
4f
–1
10 4p
8
6
4
4s
2 5p
–2
10 5d
8
6 5s
4
2
–3
10
8
6
–4
6s
4⋅10
0 200 400 600 800 1000 1200 1400 1600
Fig. 277. Re. Atomic subshell photoionization cross sections for photon
296 2.11 Nonmagnetic transition metals (Re) [Ref. p. 337
40
30 Re
20
10 9
8
7
6
5
4
3
2
19
8
7
6
5
4
3
–1
10 9
8
7
6
5
4
3
2
Fig. 278. Re. Calculated atomic
–2 5d-subshell cross section near the
10 Cooper minimum [85Y].
0 50 100 150 200 250 300 350 400
Re 4f7/2
4f7/2 Re(0001)
40.1
4f5/2
4f5/2
Intensity I
2.4
54 52 50 48 46 44 42 40 38 36 34
Binding energy Eb [eV] 44.0 43.5 43.0 42.5 42.0 41.5 41.0 40.5 40.0 39.5 39.0 38.5
Fig. 280. Re. XPS data showing the region of the spin-
orbit-split 4f core levels taken with unmonochromatized Fig. 281. Re(0001). Photoelectron spectrum in normal
AlKα radiation [79W]. For angle-integrated spectra emission within the range of the 4f core levels excited
taken with different photon energies from with photons of hν = 102 eV. Overall energy resolution
polycrystalline Re foil see also [80F2]. was about 250 meV [89M]. See also [95M].
Re
4f7/2
4f5/2
NNN
4d5/2
4d3/2
4p3/2
4p1/2
4s
5s
1200 1100 1000 900 800 700 600 500 400 300 200 100 0
Fig. 279. Re. XPS overview spectrum taken with unmonochromatized MgKα radiation [95M]. See also [80F2]. For
spectra obtained with monochromatized AlKα radiation see [95M].
Re(0001) Re(0001)
θ = 45°
40°
35°
30°
25°
44.0 43.8 43.6 43.4 43.2 43.0 42.8 42.6 42.4 42.2 42.0 41.8 41.6
a Binding energy Eb [eV] 20°
15°
10°
5°
0°
44.0 43.8 43.6 43.4 43.2 43.0 42.8 42.6 42.4 42.2 42.0 41.8 41.6
b Binding energy Eb [eV] EF
Fig. 282. Re(0001). Normal-emission spectrum of the
4f5/2core level component taken with hν = 102 eV and –17 –15 –13 –11 – 9 – 7 – 5 – 3 –1 0 1
reproduced (data points) in both panels. Top (a): the
spectrum can be well described by one Doniach-Sunjic Fig. 285. Re(0001). Photoelectron spectra taken at hν =
function (solid line). Bottom (b): Describing the same 21.2 eV for different emission angles θ along the
spectrum by two Doniach-Sunjic functions yields a ΓAHK bulk mirror plane [79B3].
surface core level shift smaller than 0.125 eV [89M].
For Figs. 283, 284 see next page
1.0
Re
0.9
0.8
0.7
0.6
Reflectivity R
0.5
0.4
0.3
0.2 Fig. 283. Re. Experimental

obtained from different experi-
0.1
ments [81W1]. For details and
tables of "most recommended"
data see [81W1].
0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0
20
Re
18
16
14
E II c E⊥c
12
10
ε2
8
4
Fig. 284. Re. Experimental ε2 data
2 [81W1] for light polarization
vector parallel (solid line) and
perpendicular (dashed) to the c-
0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 axis. See also legend to Fig. 283.
Re(0001)
θ = 45°
EF
θ = 35°
EF
θ = 25°
EF
θ = 15°
EF
θ = 5°
Fig. 286. Re(0001). Photoelectron spectra taken at hν =

EF 16.8 eV for different emission angles θ along the
ΓAHK bulk mirror plane [79B2].
–14 –12 –10 –8 –6 –4 –2 0 2
Ref. p. 337] 2.11 Nonmagnetic transition metals (Os) 301
2.11.17 Os (Osmium) (Z = 76)
Lattice: hcp. a = 2.735 Å, c = 4.319 Å, c/a 1.579 [71L]

Brillouin zone: see section 1.3 of this volume
Work-function:
φ (poly) = (5.9 ±0.3) eV [95H]
Table 24. Os. Core-level binding energies (in eV relative to EF). Estimated error ± 0.5 eV [95H, 95M].
ns1/2 np1/2 np3/2 nd3/2 nd5/2 nf5/2 nf7/2
n=4 658.2 549.1 470.7 293.1 278.5 53.4 50.7

n=5 88.0 58.0 44.5 – – – –
Figures for 2.11.17

40
20 Os
10
8
6
4
4f
2
1
8
6
4
4d
2 4f
10
–1 4p
8
6
4
4s
2 5p
–2 5d
10 8
6 5s
4
2
–3
10 8
6
–4
6s
4⋅10
0 200 400 600 800 1000 1200 1400 1600
Fig. 287. Os. Atomic subshell photoionization cross sections for photon
302 2.11 Nonmagnetic transition metals (Os) [Ref. p. 337
40
30 Os
20
10 9
8
7
6
5
4
3
19
8
7
6
5
4
3
–1
10 9
8
7
6
–2
4⋅10
0 50 100 150 200 250 300 350 400
Fig. 288. Os. Calculated atomic 5d-subshell cross section near the Cooper minimum [85Y].
For Figs. 289, 290 see next pages
1.0 20.0
Os Os
17.5
0.8
15.0
10 ε2
0.6 12.5
Reflectivity R
10.0
0.4
7.5
–1
ε2
ε2 ⋅10
0.2 5.0
2.5
0 5 10 15 20 25 30
Photon energy hν [eV] 0 5 10 15 20 25 30
Fig. 291. Os. Experimental normal-incidence
reflectivity data obtained from different experiments Fig. 292. Os. Experimental ε2 spectrum [81W1].
[81W1]. For details and tables of "most recommended"
data see [81W1].
4f7/2
Os
4f5/2
NNN
4d5/2
4d3/2
Intensity I
4p3/2
4p1/2
4s
5p
1200 1100 1000 900 800 700 600 500 400 300 200 100 0
Fig. 289. Os. XPS overview spectrum taken with unmonochromatized MgKα radiation [95M]. For results obtained
with monochromatic AlKα radiation see also [95M].
Os(0001) 4f7/2
4f5/2
55.0 54.5 54.0 53.5 53.0 52.5 52.0 51.5 51.0 50.5 50.0 49.5
S
51.75 51.50 51.25 51.00 50.75 50.50 50.25 50.00 49.75 49.50
Fig. 290. Os(0001). Top: Photoelectron spectrum in normal emission within the energy range of the 4f core levels
excited with hν = 110 eV [89M]. Bottom: Decomposition of the 4f7/2 core level spectrum taken at hν = 110 eV into
bulk (B) and surface (S) emission [89M].
1.20
1.15
Os
1.10
1.05
1.00
0.95
EF
0.90
0.85
0..80
0.75
0.70
Energy E [Ry]
0.65
0.60
0.55
0.50
0.45
0.40
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0
Γ T K T' M Σ Γ ∆ A,M U L,K P H S' L R A S H
Wavevector k
Fig. 293. Os. Relativistic band structure calculated by the linear-MTO method including spin-orbit coupling [75J1].
35.0 14
Os
32.5 13
30.0 12
27.5 11
25.0 10
22.5 9
DOS [states (Ry atom) ]

–1
–1
20.0 8
17.5 7
15.0 6
12.5 5
10.0 4
7.5 3
5.0 2
2.5 1
EF
0 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
Energy E [Ry]
Fig. 294. Os. Density of states calculated from the band structure shown in
Fig. 293 [75J1]. NOS is the integrated number of electrons per atom.
Ref. p. 337] 2.11 Nonmagnetic transition metals (Ir) 307
2.11.18 Ir (Iridium) (Z = 77)

Work-function:
φ (100) (1x1) = 6.1 ± 0.1 eV [92D1]
φ (100) (5x1) = 5.9 ± 0.1 eV [92D1]
φ (110) = 5.4 ± 0.3 eV [95H]
φ (111) = 5.8 ± 0.3 eV [95H]
Table 25. Ir. Core-level binding energies (in eV relative to EF). Estimated error ± 0.5 eV [95H]. See also
[95M].
ns1/2 np1/2 np3/2 nd3/2 nd5/2 nf5/2 nf7/2
n=4 691.1 577.8 495.8 311.9 296.3 63.8 60.8
n=5 95.2 63.0 48.0 – – – –
Table 26. Ir. Experimental and calculated critical point energies (in eV with
respect to EF).
Energy Experiment Calculation
level [80V1] [82N]
Γ8+ –4.07(8) –3.94
Γ7+ –3.18(8) –3.06
Γ8+ –1.04(5) –1.00
Γ7– 15.2(5) 14.67
Γ6– 18.92
19.5(5)
Γ8– 19.49
L4+,5+ –4.25 (10) –4.27
L6+ –3.35 (10) –3.39
L6– –1.0 (2) –0.92
L6+ 7.6(5) 7.44
L6– 14.5(5) 13.54
X6+ 10.5(5) 10.80
308 2.11 Nonmagnetic transition metals (Ir) [Ref. p. 337
Figures for 2.11.18
40
20 r
10
8
6
4
4f
2
18
6
4
4d
2 4f
10
–1 4p
8
6
4
4s
2 5p
5d
–2
10
8
6 5s
4
2 Fig. 295. Ir. Atomic subshell

–3 photoionization cross sections for
10
8 photon energies from 0 to 1500 eV
6 6s [85Y].
–4
4⋅10
0 200 400 600 800 1000 1200 1400 1600
40
30 r
20
10 9
8
7
6
5
4
3
19
8
7
6
5
4
3
–1
10 9
8 Fig. 296. Ir. Photoionization cross
7
6 section for the 5d subshell near the
–2 Cooper minimum [85Y].
4⋅10
0 50 100 150 200 250 300 350 400
4f7/2
r
4f5/2
NNN
4d5/2
4d3/2
4p3/2
4p1/2
4s
5p
1200 1100 1000 900 800 700 600 500 400 300 200 100 0
Fig. 297. Ir. Overview XPS spectrum taken with unmonochromatized MgKα radiation [95M]. For data taken with
4f7/2 r
r 60.9 eV
4f5/2
63.9 eV
DOS
EF
75 73 71 69 67 65 63 61 59 57 55 –10 –8 –6 –4 –2 0 2
Binding energy Eb [eV] Initial state energy Ei [eV]
Fig. 298. Ir. XPS data showing the region of the spin- Fig. 299. Ir. Valence band XPS photoelectron spectrum
orbit-split 4f core levels taken with unmonochromatized taken with monochromatized (0.5 eV) AlKα radiation
MgKα radiation [95M]. For data measured using (closed circles) [74S2], compared with a smoothed
monochromatized AlKα radiation and a line-shape version of the occupied DOS calculated for bands
analysis see [74H1] and [95M]. obtained from the combined interpolation scheme, see
also Fig. 305 [74S1, 74S2]. Valence band XPS spectra
from Ir(100) are reported with high energy resolution
(0.4 eV) as a function of the electron emission angle θ
in the (100) and (110) mirror planes in [92K].
r r
EF EF
–12 –10 –8 –6 –4 –2 0 2 –12 –10 –8 –6 –4 –2 0

Fig. 300. Ir. Angle-integrated photoelectron spectrum Fig. 301. Ir. Angle-integrated photoelectron spectrum
taken with hν = 40.8 eV from a polycrystalline film taken with hν = 21.2 eV from a polycrystalline film
[86W2]. [86W2]. See also [80V2].
1.0
r
0.9
0.8
0.7
0.6
Reflectivity R
0.5
0.4
0.3
0.2 Fig. 302. Ir. Experimental normal-

incidence reflectivity data obtained
from different experiments
0.1
[81W1]. For details and tables of
"most recommended" data see
[81W1].
0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0
20
r
18
16
14
12
10
573 K
2 Fig. 303. Ir. Experimental ε2
313 K
Fig. 302.
0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0
14
r
12
10
4
Energy E [eV]
2
EF
0
–2
–4
–6 Fig. 304. Ir. Model band structure

calculated within the combined
–8 interpolation scheme. Spin-orbit
coupling and other relativistic
– 10 corrections are included [74S1].
Γ X W L Γ K X
Wavevector k
2.50 0.50
r
2.25 0.45
2.00 0.40
1.75 0.35

–1
–1
1.50 0.30
(× 5)
1.25 0.25
1.00 0.20
0.75 0.15
0.50 0.10
0.25 0.05
Fig. 305. Ir. Density of states
EF calculated from the band structure
0 0 shown in Fig. 304 [74S2].
–10 – 8 –6 –4 –2 0 2 4 6 8 10 12
3 4
20
15
5 r 2 3' 3
1 4
1
18 1
15
2
16 2' 4
2' 3
1
2' 1 2' 2' 1
14 1
4
5'
12 4 1
1 5'
1
10 1 1
3 1
8 1 1
3
1 1
3
6
Energy E [eV]
4 2
4' 1
4'
2 5 2 1' 2 5
EF 1 3 2 4
2 2
0 2 1 2' 12 2 4 3
3
12 5 1 2
–2 1 3
3 4 3
25' 25'
3
–4
1 3 1 1
3 2
2' 4 1
–6 3
3 2'
1 1
–8 1 1 1 1
1 1 1
1
– 10
1 1
– 12
Wavevector k
Fig. 306. Ir. Scalar relativistic band structure based on the self-consistent
lattice potential of a fully relativistic calculation [82N]. Symmetry labels
refer to representation in single group notation.
22
3+4
7
r 6
4+5 5 5
20 – 6 8–
8 –
6
6– 3+4 5
18 6 6–
5
16 6 7
7 5 7–
6 3+4
7– 6– 5
5
14 7 –
6 5 7–
12 6– 5 5
6–
6+ 6
10 5
6+
6
5
8 7 3+4 5
6+
5 5
Energy E [eV]
6
5
4 3+4
6– 6–
7+ +
2 5 7 57
6+ 4++5+ 6+
3+4 5 5
EF 7 5 +
4+5 5
0 6
– +
8 +
7 + 6 8 7+
6 6 3+4 6 5
5 5
–2 7 5
7+ 6 7+ 5
6 3+4 6+
8+ 8+ 5 5
7
–4 3+4 6
7 6 4+5 5
5 4++5+ 5 5
–6 7 + 7
3+4 6+
6+ 5 7+
6 5 5 5
–8 6+
6
–10 6+
+
6
–12
Wavevector k
Fig. 307. Ir. Fully relativistic band structure [82N]. Symmetry labels refer to
representations in double group notation. See also [96B].
2.0 20
r 19
r (111) 6–
1.8 ∆E = 0.8 ± 0.3 eV
18
total
1.6 17
16
1.4
15 8 7–
1.2 14
13
1.0
12
0.8 11
10
0.6
9 7
0.4 8
16.4 eV
7
0.2 EF
6 15.1 eV
0
DOS [states (atom eV) ]
–1
5 17.6 eV
0.4
Energy E [eV]
s 4
0.2 EF 3
0 2
0.4 1
6
p 5 EF
0.2 EF 0
8+
0 –1 4
1.6 –2
d –3 3 7+
1.4
–4 2
1.2 8+
–5
1.0 –6
–7 1
0.8 –8
0.6 –9
–10 6+
0.4
–11
0.2 EF –12
Γ Λ L
0 Wavevector k
0.4
f Fig. 309. Ir(111). Band structure along ΓL. Solid and
0.2 EF
dotted lines represent calculation [82N] shown also in
0 Fig. 307. Broken lines show empty calculated bands
–12 –9 –6 –3 0 3 shifted to higher energies by 0.8 eV to better match
Energy E – EF [eV] experimental results. Experimental band mapping data
are marked by various empty and filled symbols,
Fig. 308. Ir. Total DOS (top) and s,p,d,f-like partial respectively. Vertical arrows indicate direct transitions
densities of states calculated with the energy band labeled by the corresponding photon energies [87M].
structure shown in Fig. 307 [82N]. All data taken with circularly polarized light. For details
see [87H].
25 25
24 24
23 r (111) 3 23
22 22
21 21
20 3 20
19 1 19
18 18
17 17
2
Energy E [eV]
16 3 16
15 15
3
14 14
13 1 2 13
12 12
11 hν = 16 eV 11
10 10
1 9
9
8 8
Energy E [eV]
3 7
7
+ – –
6 6
– +
5 5
0 0.1 0.2 0.3 0.4 0.5 0.6
4 A B C D F Im kz
3
2 Fig. 310. Ir(111). Relativistic bulk
1 bands calculated along ΓL with
EF
0 symmetry types Λ6 (solid lines) and
–1
–2
Λ4+5 (long-dashed). Inclusion of
–3 the imaginary part of the potential
–4 yields the short-dashd empty bands
–5 (labeled 1, 2, 3) and the associated
–6 imaginary parts of the wavevector
–7 shown in the right-hand-side panel.
–8 The various symbols shown below
–9 EF represent experimental band
–10 mapping results. Vertical lines
Γ Λ L
Wavevector k indicate direct transitions at hν =
16 eV [89T]. See also Fig. 317.
r (111) r(100)–(1×1)
EF
0
–1
–2
–3
–4
Fig. 311. Ir. Experimental band mapping results (open
and filled circles) along ΓL and ΓX [80V1]. Arrows
–5
denote Fermi level crossings derived from various
experiments, solid lines are calculated bands. For details
–6 see [80V1].
L Γ X
Wavevector k
←
hν = 28 eV
r(100)–(1×1) Fig. 312. Ir(100). Normal-emission photoelectron
spectra collected at various photon energies hν from the
(1x1) unreconstructed surface [80V1]. See also [80V2].
26
Band dispersion indicated by dashed lines.
24
r(100)–(5×1)
hν = 27 eV
23
22 26
25
24
21 23
20 21
19 20
19
18
18.5
17.5 18
17
17
16 eV
16
15
14
EF
13 eV
–9 –8 –7 –6 –5 –4 –3 –2 –1 0
EF Fig. 313. Ir(100). Similar to Fig. 312 but spectra

collected from the reconstructed (5x1) surface [80V1].
–10 – 9 – 8 – 7 – 6 – 5 – 4 – 3 – 2 –1 0 See also [80V2].
r(100)–(1×1) r(100)–(1×5)
θ = 66° θ = 66°
60° 60°
50°
50°
42° 40°
38°
30°
16°
18°
10°
10°
0°
0°
–12°
–10°
–16°
–16°
4 6 8 10 12 14 16 18 20 22 24 4 6 8 10 12 14 16 18 20 22 24
Energy E – EF [eV] Energy E – EF [eV]
θ = 66° θ = 66°
60° 60°
50° 50°
40°
34°
30° 30°
24° 20°
10° 10°
0° 0°
–10°
–10°
–16° –16°
4 6 8 10 12 14 16 18 20 22 24 4 6 8 10 12 14 16 18 20 22 24
Energy E – EF [eV] Energy E – EF [eV]
Fig. 314. Ir(100). Top panels: target current spectra from the unreconstructed (1x1) and the reconstructed (1x5)
surfaces. Bottom panels: corresponding first derivatives. The numbers on the right side of each spectrum give the
angle of electron incidence in the ΓXUL azimuth [92D1].
C
r(111) r(111)
hν = 23 eV B
A
22
Total intensitiy I
D
21
EF
0 C
0.8
20 D A
0.6
0.4
0.2
Polarization P
0
19 F
– 0.2
18 B
– 0.4
C
– 0.6
17
– 0.8 EF
16
– 1.0
C
14
11.5
B
11 A
Partial intensities I+, I–
10.5
D
10
9.5 F
9 eV
ss
EF
EF
0
–9 –8 –7 –6 –5 –4 –3 –2 –1 0 –6 –5 –4 –3 –2 –1 0 1
Fig. 315. Ir(111). Normal-emission photoelectron Fig. 317. Ir(111). Normal-emission photoelectron
spectra collected at various photon energies hν [80V1]. spectra excited by normally incident circularly
See also [80V2]. ss denotes a surface state. polarized light at hν = 16 eV [87M]. Top panel shows
total electron intensity, bottom panel gives partial intensities excited with different spin directions (filled symbols:
spin up, open symbols: spin down). Middle panel shows the resulting electron spin polarization [87M]. See also
[87M] for normal-emission data taken at various photon energies. See also Fig. 310.
r(111)
ΓLW
B C
A
θ = 0°
3°
6°
9°
30°
EF
–15.0 –12.5 –10.0 –7.5 – 5.0 –2.5 0

Fig. 316. Ir(111). HeI-excited photoelectron spectra collected at different

electron exit angles θ [86M]. The features labeled A, B, C are due to
secondary electron emission, compare Fig. 318.
A r (111)
ΓLW
B
θ = 0°
6°
10°
12.5°
15°
20°
25°
30°
35°
40°
45°
50°
5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0

Energy E [eV]
Fig. 318. Ir(111). Angle-resolved secondary electron emission spectra taken at

various exit angles θ along the ΓLW bulk azimuth [86M]. Primary electron
energy 40 eV. E w.r. to EF.
A
r (111)
ΓLK
θ = 0°
10°
15°
25°
40°
A
ΓLU
θ = 0°
10°
40° Fig. 319. Ir(111). As Fig. 318 but

with electron emission angle θ
45° along ΓLK (top) and ΓLU
(bottom), respectively [86M]. For
a detailed interpretation in terms of
50° the bulk band structure see [86M].
Primary electron energy 40 eV. E
w.r. to EF.
5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0
Energy E [eV]
Ref. p. 337] 2.11 Nonmagnetic transition metals (Pt) 323
2.11.19 Pt (Platinum) (Z = 78)

Work-function:
φ (poly) = (5.5 ± 0.3) eV [95H]
φ (100) (1x1) = (5.5 ± 0.2) eV [92D1]
φ (100) (5x20) = (5.4 ± 0.2) eV [92D1]
φ (111) = (5.9 ± 0.3) eV [95H]
Table 27. Pt. Core-level binding energies in eV relative to EF. Typical scatter between different sources is
± 0.5 eV [95H]. See also [95M].
ns1/2 np1/2 np3/2 nd3/2 nd5/2 nf5/2 nf7/2
n=4 725.4 609.1 519.3 31.6 314.6 74.7 71.1
n=5 101.7 65.3 51.7 – – – –
Table 28. Pt. Experimental and calculated energies at critical points of the bulk band structure (in eV,
with respect to EF).
Critical Experiments Theory
point [80T] a) [84L] b) [84L, 84E2]
Γ8+ –4.08(7) –4.12(10) –4.11
Γ7+ –2.8(1) –2.79(5) –3.07
Γ8+ –1.4(1) –1.49(3) –1.40
Γ6– – +19.2 c) +18.5
X7+ –0.45(7) –0.38(3) –0.32
X6+ – +9.7(5) d) +9.0
L6+ – –0.95(5) –0.92
L 6– – –0.34(5) –0.36
L4+, 5+ – +0.3(2) d) +0.2
a) ARUPS; b) ARUPS; c) ARUPS [85W1]; d) IPES [88D].
324 2.11 Nonmagnetic transition metals (Pt) [Ref. p. 337
Figures for 2.11.19
2
10 8
6
4 Pt
2
5d
10 8
6
4
4f
2
18
6
4
4d
2 4f
–1
10 8 4p
6
4 4s
2
5d
5p
–2
10 8
6 5s
4
2
–3
10 8
6
4
Fig. 320. Pt. Atomic subshell
6s photoionization cross sections for
2
–4
10 [85Y].
0 200 400 600 800 1000 1200 1400 1600
40
30 Pt
20
109
8
7
6
5
4
1
9
8
7
6
5
4
3
2
Fig. 321. Pt. Photoionization cross
section for the 5d subshell near the
–1
Cooper minimum [85Y]. For
10 9 experimental data of bulk Pt in the
8
–2 energy range 10…25 eV see
6⋅10 [93V].
0 50 100 150 200 250 300 350 400
Pt 4f7/2
4f5/2
NNN
4d5/2
4d3/2
4p3/2
4s 4p1/2
5p
1200 1100 1000 900 800 700 600 500 400 300 200 100 0
Fig. 322. Pt. Overview XPS spectrum taken with unmonochromatized MgKα radiation [95M]. For results with
4f7/2 Pt(111)
Pt 4f5/2 71.2 eV
74.5 eV
s
b
Intensity I
85 83 81 79 77 75 73 71 69 67 65
Binding energy Eb [eV] 73.0 72.5 72.0 71.5 71.0 70.5 70.0 69.5 69.0
Fig. 323. Pt. XPS data showing the region of the spin-
orbit-split 4f core levels taken with unmonochromatized Fig. 324. Pt(111). Decomposition of the 4f7/2 core level
MgKα radiation [95M]. For data measured using photoemission into bulk (b) and surface (s) component
monochromatized AlKα radiation and a line-shape [00R]. See also [86D2] and[82B1]. For similar data
analysis see [74H1]. See also [95M]. from the (110)-(1x2) surface see [82B1] and [02J]. For
PtxPd1-x(111) surfaces see [02R2].
Pt
DOS
Fig. 325. Pt. Valence band XPS spectrum taken with

monochromatized (0.5 eV) AlKα radiation (closed
circles) [74S2], compared with a smoothed version of
the occupied DOS calculated from the combined
interpolation scheme, see also Fig. 329 [74S1, 74S2].
For a comparison between theory and experiment see
also [76H2]. Results of inverse photoemission in the
EF
20…40 eV range are presented for a polycrystalline
sample in [82B2].
–10 –8 –6 –4 –2 0 2
1.0
Pt
0.9
0.8
0.7
0.6
Reflectivity R
0.5
0.4
0.3
Fig. 326. Pt. Experimental normal-
0.2 incidence reflectivity data obtained
from different experiments
[81W1]. For details and tables of
0.1 "most recommended" data see
[81W1]. For theoretical results see
[01K1].
0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0
8
Pt
7
5
ε2
3 ε2 ⋅ 10
–1
2
scale
change
1 Fig. 327. Pt. Experimental ε2
Fig. 326. For theoretical results see
[01K1].
0 2 4 6 8 10 15 20 25 30 35 40 45 50
14
Pt
12
10
4
Energy E [eV]
2
EF
0
–2
–4
–6
Fig. 328. Pt. Model band structure
calculated within the combined
–8 interpolation scheme. Spin-orbit
coupling and other relativistic
– 10 corrections are included [74S1].
Γ X W L Γ K X
Wavevector k
3.00 0.60
Pt
2.75 0.55
2.50 0.50
2.25 0.45
2.00 0.40

–1
–1
1.75 0.35
1.50 0.30
(× 5)
1.25 0.25
1.00 0.20
0.75 0.15
0.50 0.10
0.25 0.05 Fig. 329. Pt. Density of states

EF calculated from the band structure
0 0 shown in Fig. 328 [74S2].
–10 –8 –6 –4 –2 0 2 4 6 8 10 12
4.4
4.3 Pt
4.2
4.1
4.0
3.9
3.8
3.7
3.6
Energy E [Ry]
3.5
3.4
EF
3.3
3.2
3.1
3.0
2.9
2.8 Fig. 330. Pt. Fully relativistic band
2.7 structure based on density-
2.6 functional theory in the local-
density approximation [00T1]. See
2.5 also [96B].
Γ ∆ X Z W Q L Λ Γ Σ K L U s X
Wavevector k
0
Pt(100) EF
–1 For Fig. 331 see next page
–2
–3
–4
–5
–6
–7
–8
Fig. 332. Pt(100). Experimental bulk band dispersion
(filled circles) along the ΓX direction [80T]. See also
–9
[84L], [84W1] and [88D]. For gap emission in
ultraviolet photoemission experiments see also [89C].
–10 For the surface bands of Pt(100) see [95S].
Γ ∆ X
Wavevector k
26 26
1 Pt(111) 2 3
24 24
22 22
20 20
1 3
18 18
Energy E [eV]
2
3
16 16
3
14 1 14
2
12 12
10 10
1
Energy E [eV]
8 8
6 6
0 0.1 0.2 0.3 0.4 0.5 0.6
4
Im kz
2
EF
0
–2
–4
–6
–8
–10
Γ Λ L
Wavevector k
Fig. 331. Pt(111). Relativistic bulk bands calculated shown in the right-hand-side panel. The various
along ΓL with symmetry types Λ6 (solid lines) and Λ4+5 symbols shown below EF represent experimental band
(dashed). Inclusion of the imaginary part of the mapping results. Vertical lines indicate direct transitions
potential yields the dotted empty bands (labeled 1, 2, 3) at hν = 17 eV [89T].
and the associated imaginary parts of the wavevector
0
Pt EF
–
– 0.5 6
6+
–1.0 4+5 7
8+
–1.5
6
–2.0
6
–2.5
6
–3.0 7 Fig. 333. Pt. Experimental valence

6+ 7+
band mapping results along ΓL
–3.5 and ΓX (various open and filled
6 symbols resulting from different
6
–4.0 experiments) [85W1] compared to
the band structure calculation of
8+
4+5 [84E2]. Symmetry labels in double
–4.5 4+ + 5+ 7 group notation. For data above EF
see [85W1] and [88D].
–5.0
L Λ Γ ∆ X
Wavevector k
6
Pt(110)
5
4 5,1
2 6– ,4'
7+,5
1
EF 6+,5
0
5,2
–1 7+,2
8+,12
5,4
Energy E [eV]
–2
5,2 5,4
–3 5,3
7+,25'
5,1
–4
8+,25'
–5 5,3
5,1
–6 7+,3
5,1
6+,1 Fig. 334. Pt(110). Bulk band mapping results along
–7
ΓKX (symbols) [86V] compared to calculated bands
–8 from [84E2]. Symmetry labels refer to double group,
single group notation. Data are recorded for the (1x2)
–9 reconstructed surface using spin-polarized
photoemission with circularly polarized, normally
–10 incident light [86V]. For other spin-resolving
6+,1
photoemission experiments see [95I, 96I].
–11
Γ Σ K X
Wavevector k
0.5
EF Pt(111) Pt(001)
0
–0.5 4,3 5,3
–1.0
–1.5
6,1 6,3
–2.0
–2.5
–3.0 6,3
–3.5 6,3
4,3 5,3
–4.0
–4.5 6,1
EF
–5.0
L Λ Γ
Wavevector k –3.5 –3.0 –2.5 – 2.0 – 1.5 – 1.0 – 0.5 0 0.5
Fig. 335. Pt(111). Bulk band mapping results (filled
circles) from spin-resolved normal-emission Fig. 337. Pt(001). Normal-emission photoelectron
photoelectron spectra excited with circularly polarized spectrum taken at hν = 16.85 eV [84L].
light [89G1]. Solid lines represent band structure
calculation of [84E2]. Symmetry labels refer to double
group, single group notation. Different symbols are
experimental data from various sources.
Pt(100) hν = 20.5 eV
20.0
19.5
19.0 hν = 30 eV
18.5 28
26
18.0
25
24
16.0 23
22
14.0 21 eV
11.0 eV
EF EF
–7 –6 –5 – 4 – 3 – 2 –1 0 1 2 –7 –6 –5 –4 –3 –2 –1 0 1
Fig. 336. Pt(100). Normal-emission photoelectron spectra recorded at different photon energies hν [80T].
Pt(100) Γ X
10
Pt(001) ΓXUL
9
(1×1)
7
EF

6 S
5 B
S
4
B
(5 × 20)
3
EF 2
1
B
EF = 0
0 0.25 0.50 0.75 1.00 1.25
Pt(111) Wavevector kII [Å–1]
Fig. 339. Pt(001). Experimental final state energies as a

function of k|| derived from angle-dependent inverse
EF photoemission spectra. Unshaded areas denote gaps of
the projected bulk band structure. Label B and S denote
–2 –1 0 1 2 3 4 5 6 7 8 bulk and surface character, respectively. Full (empty)
Energy E [eV] symbols result from prominent (weak) spectral features.
Solid lines connect data points to guide the eye. The
Fig. 338. Pt(100), Pt(111). Normal-incidence dashed line results from a calculation using theoretical
isochromat spectra from the unreconstructed (100)- bulk bands and assuming bulk direct transitions [88D].
(1x1) surface (top), the reconstructed (100)-(5x20)
surface (middle) and Pt(111) (bottom). Photon energy
9.5 eV [88D]. For results from target-current
spectroscopy at Pt(100) see [92D1].
Pt(111) hν = 29 eV
hν = 29 eV
26
26
22 22
18
18
17
17
16
16
15 15
14 14
13 eV
13 eV
EF EF
– 10 – 9 – 8 – 7 – 6 – 5 – 4 – 3 – 2 –1 0 1 2 – 10 – 9 – 8 – 7 – 6 – 5 – 4 – 3 – 2 –1 0 1 2
Fig. 340. Pt(111). Normal-emission photoelectron spectra recorded with p-polarized (left) and s-polarized (right)
light at various photon energies hν [80M].
Pt(111) hν = 22 eV
EF
hν = 23 eV
EF
hν = 24 eV
EF
X hν = 25 eV
Fig. 341. Pt(111). Normal-

emission photoelectron spectra
recorded at photon energies
between 22 and 25 eV. The arrows
indicate peaks due to secondary
electron emission [89T]. For spin-
resolving photoemission experi-
EF ments see [84E1, 85O, 88S2].
–18 –16 –14 –12 –10 –8 –6 –4 –2 0

Pt(111)
hν = 24.9 eV
23.9
23.0
22.0
21.0
20.0
19.0
18.1
17.1
16.1
15.1
14.2
13.2
12.2 eV
Fig. 342. Pt(111). Normal-emission photoelectron
spectra recorded at different photon energies hν
showing dispersion of bulk bands (dashed lines) and
EF
strong intensity resonances between hν = 20 and 22 eV
[85W1]. For angle-dependent spectra see also [92D2].
–5 –4 –3 –2 –1 0
2.11 Nonmagnetic transition metals (References) 337
63W Wyckoff, R. W. G.: Crystal Structures, John Wiley & Sons, New York, 2nd Ed., 1963.
71L Landolt-Börnstein (New Series) Vol. III/6, Springer, Berlin-Heidelberg 1971.
72P Papaconstantopoulos, D. A., Anderson, J. R., McCaffrey, J. W.: Phys. Rev. B 5 (1972) 1214.
73C Christensen, N. E.: Phys. Status Solidi (b) 55 (1973) 117.
73F Feuerbacher, B., Fitton, B.: Phys. Rev. Lett. 30 (1973) 923.
73I Iverson, R. J., Hodges, L.: Phys. Rev. B 8 (1973) 1429.
74C1 Christensen, N. E., Feuerbacher, B.: Phys. Rev. B 10 (1974) 2349.
74C2 Christensen, N. E., Feuerbacher, B.: Phys. Rev. B 10 (1974) 2373.
74H1 Hüfner, S., Wertheim, G. K., Buchanan, D. N. E., West, K. W.: Phys. Lett. 46A (1974) 420.
74H2 Hüfner, S., Wertheim, G. K., Buchanan, D. N. E.: Solid State Commun. 14 (1974) 1173.
74S2 Smith, N. V., Wertheim, G. K., Hüfner, S., Traum, M. M.: Phys. Rev. B 10 (1974) 3197.
75J1 Jepsen, O., Andersen, O. K., Mackintosh, A. R.: Phys. Rev. B 12 (1975) 3084.
75J2 Jepsen, O.: Phys. Rev. B 12 (1975) 2988.
76C1 Christensen, N. E.: Phys. Rev. B 14 (1976) 3446.
76C2 Cinti, R. C., Alkhouri, E., Chakraverty, B. K., Christensen, N. E.: Phys. Rev. B 14 (1976)
3296.
76D Das, S. G.: Phys. Rev. B 13 (1976) 3978.
76H1 Höchst, H., Hüfner, S., Goldmann, A.: Solid State Commun. 19 (1976) 899.
76H2 Höchst, H., Hüfner, S., Goldmann, A.: Phys. Lett. 57A (1976) 265.
76P Penchina, C. M.: Phys. Rev. B 14 (1976) 4407.
76S Smith, R. J., Anderson, J., Hermanson, J., Lapeyre, G. J.: Solid State Commun. 19 (1976) 975.
77B Boyer, L. L., Papaconstantopoulos, D. A., Klein, B. M.: Phys. Rev. B 15 (1977) 3685.
77E Elyashar, N., Koelling, D. D.: Phys. Rev. B 15 (1977) 3620.
77F Faulkner, J. S.: Phys. Rev. B 16 (1977) 736.
77G Gimzewski, J. K., Fabian, D. J., Watson, L. M., Affrossman, S.: J. Phys. F7 (1977) L305.
77L1 Ley, L., Dabbousi, O. B., Kowalczyk, S. P., McFeely, F. R., Shirley, D. A.: Phys. Rev. B 16
(1977) 5372.
77L2 Lloyd, D. R., Quinn, C. M., Richardson, N. V.: Surf. Sci. 63 (1977) 174.
77N Noguera, C., Spanjaard, D., Jepsen, D., Ballu, Y., Guillot, C., Lecante, J., Paigne, J., Petroff,
Y., Pinchaux, R., Thiry, P., Cinti, R.: Phys. Rev. Lett. 38 (1977) 1171.
77P Platau, A., Johansson, L. I., Hagström, A. L., Karlsson, S.-E., Hagström, S. B. M.: Surf. Sci. 63
(1977) 153.
77W1 Weng, S.-L., Plummer, E. W.: Solid State Commun. 23 (1977) 515.
77W2 Weng, S.-L., Gustafsson, T., Plummer, E. W.: Phys. Rev. Lett. 39 (1977) 822.
78A Anderson, J.: Phys. Rev. B 17 (1978) 2436.
78B Braun, W., Neumann, M., Iwan, M., Koch, E. E.: Phys. Status Solidi (b) 90 (1978) 525.
78C Cardona, M., Ley, L.: Photoemission in Solids 1, Springer, Berlin 1978.
78F Fukuda, Y., Lancaster, G. M., Honda, F., Rabalais, J. W.: Phys. Rev. B 18 (1978) 6191.
78H Himpsel, F. J., Eastman, D. E.: Phys. Rev. B 18 (1978) 5236.
78L Laurent, D. G., Wang, C. S., Callaway, J.: Phys. Rev. B 17 (1978) 455.
78M Moruzzi, V. L., Janak, J. F., Williams, A. R.: Calculated electronic properties of metals: New
York, Pergamon Press, 1978.
78W1 Weng, S.-L., Plummer, E. W., Gustafsson, T.: Phys. Rev. B 18 (1978) 1718.
78W2 Willis, R. F., Christensen, N. E.: Phys. Rev. B 18 (1978) 5140.
79A Asokamani, R., Iyakutti, K., Devanathan, V.: Solid State Commun. 30 (1979) 385.
79B1 Borstel, G., Braun, W., Neumann, M., Seitz, G.: Phys. Status Solidi (b) 95 (1979) 453.
79B2 Braun, W., Meyer-Ehmsen, G., Neumann, M., Schwarz, E.: Surf. Sci. 89 (1979) 354.
79B3 Braun, W., Meyer-Ehmsen, G., Neumann, M., Schwarz, E.: Solid State Commun. 30 (1979)
605.
79D Dahlbäck, N., Nilsson, P. O., Pessa, M.: Phys. Rev. B 19 (1979) 5961.
338 2.11 Nonmagnetic transition metals (References)
79F Feibelmann, P. J., Hamann, D. R.: Solid State Commun. 31 (1979) 413.
79H Hölzl, J., Schulte, F. K.: Solid Surface Physics. Springer Tracts Mod. Phys., Vol. 85, Springer,
Berlin 1979.
79I Inglesfield, J. E.: J. Phys. B 12 (1979) L349.
79L Louie, S. G., Ho, K. M., Cohen, M. L.: Phys. Rev. B 19 (1979) 1774.
79S Steiner, P., Höchst, H., Schneider, J., Hüfner, S.: Z. Phys. B 33 (1979) 241.
79V1 Veal, B. W., Lam, D. J., Westlake, D. G.: Phys. Rev. B 19 (1979) 2856.
79V2 Vohra, Y. K., Sikka, S. K., Chidambaram, R.: J. Phys. F9 (1979) 1771.
79W Wagner, C. D., Riggs, W. M., Davis, L. E., Moulder, F. J., Muilenberg, G. E.: Handbook of
XPS Perkin-Elmer Corporation, Eden Prairie 1979.
79Z Zunger, A., Kerker, G. P., Cohen, M. L.: Phys. Rev. B 20 (1979) 581.
80A1 Asonen, H., Lindroos, M., Pessa, M., Dahlbäck, N.: Solid State Commun. 35 (1980) 69.
80A2 Amamou, A., Johnson, W. L.: Solid State Commun. 35 (1980) 765.
80C Campuzano, J. C., King, D. A., Somerton, C., Inglesfield, J. E.: Phys. Rev. Lett. 45 (1980)
1649.
80F1 Fukuda, Y., Honda, F., Rabalais, J. W.: Surf. Sci. 91 (1980) 165.
80F2 Fukuda, Y., Honda, F., Rabalais, J. W.: Surf. Sci. 93 (1980) 338.
80H Hussain, Z., Fadley, C. S., Kono, S., Wagner, L. F.: Phys. Rev. B 22 (1980) 3750.
80M Mills, K. A., Davis, R. F., Kevan, S. D., Thornton, G., Shirley, D. A.: Phys. Rev. B 22 (1980)
581.
80S1 Sen, M., Chatterjee, S.: J. Phys. F10 (1980) 985.
80S2 Smith, R. J., Williams, G. P., Colbert, J., Sagurton, M., Lapeyre, G. J.: Phys. Rev. B 22 (1980)
1584.
80T Thornton, G., Davis, R. F., Mills, K. A., Shirley, D. A.: Solid State Commun. 34 (1980) 87.
80V1 van der Veen, J. F., Himpsel, F. J., Eastman, D. E.: Phys. Rev. B 22 (1980) 4226.
80V2 van der Veen, J. F., Himpsel, F. J., Eastman, D. E.: Solid State Commun. 34 (1980) 33.
81B Borstel, G., Neumann, M., Braun, W.: Phys. Rev. B 23 (1981) 3113.
81C Campuzano, J. C., Inglesfield, J. E., King, D. A., Somerton, C.: J. Phys. C14 (1981) 3099.
81F Feder, R., Kirschner, J.: Solid State Commun. 40 (1981) 547.
81H1 Himpsel, F. J., Christmann, K., Heimann, P., Eastman, D. E.: Phys. Rev. B 23 (1981) 2548.
81H2 Höchst, H., Steiner, P., Reiter, G., Hüfner, S.: Z. Physik B 42 (1981) 199.
81K Kirschner, J., Feder, R., Wendelken, J. F.: Phys. Rev. Lett. 47 (1981) 614.
81N Nilsson, P. O., Larsson, C. G., Eberhardt, W.: Phys. Rev. B 24 (1981) 1739.
81S1 Schäfer, J., Schoppe, R., Hölzl, J., Feder, R.: Surf. Sci. 107 (1981) 290.
81S2 Smith, R. J.: Solid State Commun. 37 (1981) 725.
81W1 Weaver, J. H., Krafka, C., Lynch, D. W., Koch, E. E.: Optical properties of metals, Vol. I,
Fachinformationszentrum Physik, Karlsruhe, Germany, 1981.
81W2 Vol. II of Ref. [81W1].
82A1 Amamou, A., Turek, P., Kuentzler, R.: Solid State Commun. 43 (1982) 431.
82A2 Amamou, A., Kuentzler, R.: Solid State Commun. 43 (1982) 423.
82B1 Baetzold, R. C., Apai, G., Shustorovich, E., Jaeger, R.: Phys. Rev. B 26 (1982) 4022.
82B2 Baptist, R., Chauvet, G.: J. Phys. C15 (1982) 2313.
82B3 Blanchet, G. B., DiNardo, N. J., Plummer, E. W.: Surf. Sci. 118 (1982) 496.
82C Cerrina, F., Anderson, J. R., Lapeyre, G. J., Bisi, O., Calandra, C.: Phys. Rev. B 25 (1982)
4949.
82J Jaklevic, R. C., Davis, L. C.: Phys. Rev. B 26 (1982) 5391.
82M Miller, J. N., Lindau, I., Stefan, P. M., Weissmann, D. L., Shek, M. L., Spicer, W. E.: J. Appl.
Phys. 53 (1982) 3267.
82N Noffke, J., Fritsche, L.; J. Phys. F.: Met. Phys. 12 (1982) 921.
82R Riehle, F., Wolf, Th., Politis, C.: Z. Phys. B47 (1982) 201.
83A Abbati, I., Braicovich, L., Rossi, G., Lindau, I., del Pennino, U., Nannarone, S.: Phys. Rev.
Lett. 50 (1983) 1799.
83B1 Bylander, D. M., Kleinmann, L.: Phys. Rev. B 27 (1983) 3152.
83B2 Bertel, E., Stockbauer, R., Madey, T. E.: Phys. Rev. B 27 (1983) 1939.
83C Chatterjee, P.: Phys. Rev. B 27 (1983) 4722.

83D Dragoun, O., Fiser, M., Brabec, V., Kovalik, A., Kuklik, A., Mikusik, P.: Phys. Lett. 99A
(1983) 187.
83E Erbudak, M., Kalt, P., Schlapbach, L., Bennemann, K.: Surf. Sci. 126 (1983) 101.
83F Foord, J. S.: Surf. Sci. 129 (1983) 79.
83L Lloyd, D. R., Netzer, F. P.: Solid State Commun. 45 (1983) 1047.
83P Porte, L., Roux, L., Hanus, J.: Phys. Rev. B 28 (1983) 3214.
83S Fu, C. L., Ho, K. M.: Phys. Rev. B 28 (1983) 5480.
83W Werfel, F., Minni, E.: J. Phys. C16 (1983) 6091.
84B1 Bylander, D. M., Kleinman, L.: Phys. Rev. B 29 (1984) 1534.
84B2 Bertel, E.: Surf. Sci. 141 (1984) 355.
84C1 Chen, T. P., Wolf, E. L., Giorgi, A. L.: Phys. Rev. B 29 (1984) 6036.
84C2 Chatterjee, P.: J. Phys. F14 (1984) 2027.
84E1 Eyers, A., Schäfers, F., Schönhense, G., Heinzmann, U., Oepen, H. P., Hünlich, K., Kirschner,
J., Borstel, G.: Phys. Rev. Lett. 52 (1984) 1559.
84E2 Eckardt, H., Fritsche, L., Noffke, J.: J. Phys. F: Met. Phys. 14 (1984) 97.
84H1 Hora, R., Scheffler, M.: Phys. Rev. B 29 (1984) 692.
84H2 Höchst, H., Kelly, M. K.: Phys. Rev. B 30 (1984) 1708.
84I Ishii, H., Miyahara, T., Hanyu, T., Yamaguchi, S.: J. Phys. Soc. Jpn. 53 (1984) 2151.
84J Jansen, H. J. F., Freeman, A. J.: Phys. Rev. B 30 (1984) 561.
84L Leschik, G., Courths, R., Wern, H., Hüfner, S., Eckard, H., Noffke, J.: Solid State Commun. 52
(1984) 221.
84N Nyholm, R., Schmidt, May, J.: J. Phys. C17 (1984) L113.
84S Speier, W., Fuggle, J. C., Zeller, R., Ackermann, B., Szot, K., Hillebrecht, F. U., Campagna,
M.: Phys. Rev. B 30 (1984) 6921.
84W1 Wern, H., Leschik, G., Hau, U., Courths, R.: Solid State Commun. 50 (1984) 581.
84W2 Wertheim, G. K., Citrin, P. H., Van der Veen, J. F.: Phys. Rev. B 30 (1984) 4343.
84W3 Wesner, D. A., Johnson, P. D., Smith, N. V.: Phys. Rev. B 30 (1984) 503.
85B Barth, J., Gerken, F., Kunz, C.: Phys. Rev. B 31 (1985) 2022.
85G Guillot, C., Chaveau, D., Roubin, P., Lecante, J., Desjonquères, M. C.: Surf. Sci. 162 (1985)
46.
85L Lindroos, M.: Surf. Sci. 152/153 (1985) 222.
85O Oepen, H. P., Hünlich, K., Kirschner, J., Eyers, A., Schäfers, F., Schönhense, G., Heinzmann,
U.: Phys. Rev. B 31 (1985) 6846.
85P1 Palik, E. D. (Editor): Handbook of Optical Constants of Solids, Academic, Orlando 1985.
85P2 Park, C.: Surf. Sci. 154 (1985) 371.
85S Speier, W., Zeller, R., Fuggle, J. C.: Phys. Rev. B 32 (1985) 3597.
85W1 Wern, H., Courths, R., Leschik, G., Hüfner, S.: Z. Phys. B: Condensed Matter 60 (1985) 293.
85W2 Wei, S.-H. Krakauer, H., Weinert, M.: Phys. Rev. B 32 (1985) 7792.
85Y Yeh, J. J., Lindau, I.: Atomic Data and Nuclear Data Tables 32 (1985) 1.
86C Chelikowsky, J. R., Chan, C. T., Louie, S. G.: Phys. Rev. B 34 (1986) 6656.
86D1 Drube, W., Straub, D., Himpsel, F. J.: Phys. Rev. B 34 (1986) 8989.
86D2 Dückers, K., Bonzel, H. P., Wesner, D. A.: Surf. Sci. 166 (1986) 141.
86H Hulbert, S. L., Johnson, P. D., Weinert, M.: Phys. Rev. B 34 (1986) 3670.
86L1 Lindroos, M., Pfnür, H., Menzel, D.: Phys. Rev. B 33 (1986) 6684.
86L2 Lindroos, M., Hofmann, P., Menzel, D.: Phys. Rev. B 33 (1986) 6798.
86M Mack, J. U., Bertel, E., Netzer, F. P., Lloyd, D. R.: Z. Phys. B: Condens. Matter 63 (1986) 97.
86R Raaen, S.: Solid State Commun. 60 (1986) 991.
86V Venus, D., Garbe, J., Suga, S., Schneider, C., Kirschner, J.: Phys. Rev. B 34 (1986) 8435.
86W1 White, R. C., Fadley, C. S., Sagurton, M., Hussain, Z.: Phys. Rev. B 34 (1986) 5226.
86W2 Wittmer, M., Oelhafen, P., Tu, K. N.: Phys. Rev. B 33 (1986) 5391.
87B1 Barrett, S. D., Jordan, R. G.: Z. Phys. B: Condens. Matter 66 (1987) 375.
87B2 Benndorf, C., Bertel, E., Dose, V., Jacob, W., Memmel, N., Rogozik, J.: Surf. Sci. 191 (1987)
455.
87B3 Bartynski, R. A., Gustafsson, T.: Phys. Rev. B 35 (1987) 939.

87C Cserny, I., Kövér, L., Tóth, J., Fiser, M.: J. Phys. (Paris) Colloq. 48, Suppl. 12, C9-1017
(1987).
87G Gaylord, R. H., Kevan, S. D.: Phys. Rev. B 36 (1987) 9337.
87H Heinzmann, U.: Phys. Scr. T 17 (1987) 77.
87I Ilver, L., Kovacs, A., Kanski, J., Nilsson, P. O., Sobczak, E.: Phys. Scr. 35 (1987) 726.
87J Jugnet, Y., Prakash, N. S., Duc, Tran Minh, Poon, H. C., Grenet, G., Pendry, J. B.: Surf. Sci.
189/190 (1987) 782.
87K1 Kubiak, G. D.: J. Vac. Sci. Technol. A: 5 (1987) 731.
87K2 Krainsky, I. L.: J. Vac. Sci. Technol. A: 5 (1987) 735.
87L Lu, Z. W., Singh, D., Krakauer, H.: Phys. Rev. B 36 (1987) 7335.
87M Müller, N., Kessler, B., Schmiedeskamp, B., Schönhense, G., Heinzmann, U.: Solid State
Commun. 61 (1987) 187.
87N Neddermeyer, H., Paul, Th.: Phys. Rev. B 36 (1987) 4148.
87S Shore, J. D., Papaconstantopoulos, D. A.: Phys. Rev. B 35 (1987) 1122.
88B Blaha, P., Schwarz, K., Dederichs, P. H.: Phys. Rev. B 38 (1988) 9368.
88D Drube, R., Dose, V., Goldmann, A.: Surf. Sci. 197 (1988) 317.
88H Hu, Y., Wagener, T. J., Gao, Y., Weaver, J. H.: Phys. Rev. B 38 (1988) 12708.
88J1 Jani, A. R., Brener, N. E., Callaway, J.: Phys. Rev. B 38 (1988) 9425.
88J2 Johnson, P. D., Pan, X.: Phys. Rev. B 38 (1988) 9447.
88J3 Jeong, K., Gaylord, R. H., Kevan, S. D.: Phys. Rev. B 38 (1988) 10302.
88L Landolt-Börnstein (New Series) Vol. III/14a, Springer, Berlin-Heidelberg 1988.
88S2 Schmiedeskamp, B., Vogt, B., Heinzmann, U.: Phys. Rev. Lett. 60 (1988) 651.
88S3 Schmiedeskamp, B., Kessler, B., Müller, N., Schönhense, G., Heinzmann, U.: Solid State
Commun. 65 (1988) 665.
88S4 Smith, N. V., Chen, C. T., Tranquada, J. M., Johnson, P. D.: Phys. Rev. B 38 (1988) 12259.
88S5 Simunek, A., Veckar, J., Sobczak, E.: Phys. Rev. B 38 (1988) 8515.
88S6 Sobszak, E., Auleytner, J.: Phys. Rev. B 37 (1988) 6251.
88S7 Sebilleau, D., Suillot, C., Chauveau, D., Villette, B., Lecante, J., Desjonquères, M. C.,
Spanjaard, D., Tréglia, G.: J. Phys. C. Solid State Phys. 21 (1988) 287.
88T Tripathi, G. S., Brener, N. E., Callaway, J.: Phys. Rev. B 38 (1988) 10454.
88W Wertheim, G. K., Citrin, P. H.: Phys. Rev. B 38 (1988) 7820.
89A Andrews, P. T., Collins, I. R.: Phys. Scr. T 29 (1989) 116.
89B Barrett, S. D., Begley, A. M., Durham, P. J., Jordan, R. G.: Solid State Commun. 71 (1989)
111.
89C Courths, R., Wern, H., Leschik, G., Hüfner, S.: Z. Phys. B: Condens. Matter 74 (1989) 233.
89G1 Garbe, J., Kirschner, J.: Phys. Rev. B 39 (1989) 1530.
89G2 Goldmann, A., Rosina, G., Bertel, E., Netzer, F. P.: Z. Phys. B: Condens. Matter 73 (1989)
479.
89G3 Gaylord, R. H., Jeong, K., Dhar, S., Kevan, S. D.: J. Vac. Sci. Technol. A: 7 (1989) 2203.
89H Hu, Y., Wagener, T. J., Gao, Y., Weaver, J. H.: Phys. Rev. B 39 (1989) 8162.
89J Jeong, K., Gaylord, R. H., Kevan, S. D.: Phys. Rev. B 39 (1989) 2973.
89K Koukal, J., Sunjic, M., Lenac, Z., Conrad, H., Stenzel, W., Kordesch, M. E.: Phys. Rev. B 39
(1989) 4911.
89M Martensson, N., Saalfeld, H. B., Kuhlenbeck, H., Neumann, M.: Phys. Rev. B 39 (1989) 8181.
89P1 Pan, X., Viescas, A. J., Johnson, P. D.: Phys. Rev. B 40 (1989) 3425.
89P2 Purcell, K. G., Derby, G. P., King, D. A.: J. Phys. Condens. Matter 1 (1989) 1373.
89T Tamura, E., Piepke, W., Feder, R.: J. Phys.: Condens. Matter 1 (1989) 6469.
90J Jacob, W., Memmel, N., Bertel, E., Dose, V.: Appl. Phys. A (Solids Surf.) A50 (1990) 207.
90K1 Köver, L., Scerny, I., Brabec, V., Fiser, M., Dragoun, O., Novak, J.: Phys. Rev. B 42 (1990)
643.
90K2 Kneedler, E., Skelton, D., Smith, K. E., Kevan, S. D.: Phys. Rev. Lett. 64 (1990) 3151.
90M Morra, R. M., Almeida, F. J. D., Willis, R. F.: Phys. Scr. 41 (1990) 594.
90P Pan, X., Plummer, E. W., Weinert, M.: Phys. Rev. B 42 (1990) 5025.
90R Riffe, D. M., Wertheim, G. K., Citrin, P. H., Buchanan, D. N. E.: Phys. Scr. 41 (1990) 1009.
90S Smith, K. E., Elliott, G. S., Kevan, S. D.: Phys. Rev. B 42 (1990) 5385.
90Y Yagi, K., Higashiyama, K., Yamazaki, S., Yanashima, H., Ohnuki, H., Fukutani, H., Kato, H.:
Surf. Sci. 231 (1990) 397.
91B Blyth, R. I. R., Andrews, P. T., Barrett, S. D.: J. Phys.: Condens. Matter 3 (1991) 2827.
91C Collins, I. R., Laine, A. D., Andrews, P. T., Durham, P. J.: J. Phys.: Condens. Matter 3 (1991)
5307.
91E1 Elliott, G. S., Smith, K. E., Kevan, S. D.: Phys. Rev. B 43 (1991) 3893.
91E2 Elliott, G. S., Smith, K. E., Kevan, S. D.: Phys. Rev. B 44 (1991) 10826.
91K1 Kitajima, M., Nakamura, K., Fujitsuka, M., Shinno, H., Katoh, H., Miyahara, T.: Phys. Rev. B
44 (1991) 8338.
91K2 Kneedler, E., Smith, K. E., Skelton, D., Kevan, S. D.: Phys. Rev. B 44 (1991) 8233.
91M Matsumoto, M., Staunton, J. B., Strange, P.: J. Phys.: Condens. Matter 3 (1991) 1453.
91S1 Smith, K. E., Kevan, S. D.: Phys. Rev. B 43 (1991) 3986.
91S2 Smith, K. E., Kevan, S. D.: Phys. Rev. B 43 (1991) 1831.
91S3 Sipr, O., Vackar, J., Simunek, A.: Phys. Rev. B 44 (1991) 4832.
92B Barrett, S. D.: Surf. Sci. Rep. 14 (1992) 271.
92C Collins, I. R., Laine, A. D., Andrews, P. T.: J. Phys.: Condens. Matter 4 (1992) 2891.
92D1 Drube, R., Noffke, J., Schneider, R., Rogozik, J., Dose, V.: Phys. Rev. B 45 (1992) 4390.
92D2 Di, W., Smith, K. E., Kevan, S. D.: Phys. Rev. B 45 (1992) 3652.
92F Fuggle, J. C., Inglesfield, J. E. (eds): Unoccupied Electronic States, Vol. 69 of Topics in
Applied Physics, Springer Berlin, 1992.
92H Houston, J. E., Feibelman, P. J., O'Neill, D. G., Hamann, D. R.: Phys. Rev. B 45 (1992) 1811.
92K Klebanoff, L. E., Van Campen, D. G.: Phys. Rev. B 46 (1992) 9744.
92N Nyholm, R., Ovarfort, M., Andersen, J. N., Sorensen, S. L., Wigren, C.: J. Phys.: Condens.
Matter 4 (1992) 277.
92P Puppin, E., Vavassori, P.: J. Phys.: Condens. Matter 4 (1992) 5551.
92S Saisa, L., Kaurila, T., Vayrynen, J.: Solid State Commun. 83 (1992) 407.
92W Wu, S. C., Poirier, D. M., Jost, M. B., Weaver, J. H.: Phys. Rev. B 45 (1992) 8709.
93D Dongqui Li, Dowben, P. A., Ortega, J. E., Himpsel, F. J.: Phys. Rev. B 47 (1993) 12895.
93F Fang, B.-S., Lo, W.-S., Chen, H.-H.: Phys. Rev. B 47 (1993) 10671.
93H Hong, S. C., Lee, J. I.: Int. J. Mod. Phys. B7 (1993) 524.
93L Lundgren, E., Johansson, U., Nyholm, R., Andersen, J. N.: Phys. Rev. B 48 (1993) 5525.
93S Shin, K. S., Kim, C. Y., Chung, J. W., Lee, S. K., Park, C. Y., Kinoshita, T., Watanabe, M.,
Kakizaki, A., Ishii, T.: Phys. Rev. B 47 (1993) 13594.
93V Vavassori, P., Puppin, E.: Solid State Commun. 87 (1993) 955.
94A Andersen, J. N., Hennig, D., Lundgren, E., Methfessel, M., Nyholm, R., Scheffler, M.: Phys.
Rev. B 50 (1994) 17525.
94B Borg, A., Berg, C., Raaen, S., Venvik, H. J.: J. Phys.: Condens. Matter 6 (1994) L7.
94F Fang, B. S., Lo, W.-S., Chien, T.-S., Leung, T. C., Lue, C. Y.: Phys. Rev. B 50 (1994) 11093.
94L Lamouri, A., Krainsky, I. L.: Surf. Sci. 303 (1994) 341.
94P1 Patchett, A. J., Dhesi, S. S., Blyth, R. I. R., Barrett, S. D.: Surf. Sci. 307-309 (1994) 854.
94P2 Pervan, P., Valla, T., Milun, M.: Solid State Commun. 89 (1994) 917.
94S Samarin, S. N., Dmitrieva, O. G., Yakovlev, I. I., Ahmat, A. A., Artamonov, O. M.: Surf. Sci.
307-309 (1994) 969.
94U Unger, P., Igarashi, J., Fulde, P.: Phys. Rev. B 50 (1994) 10485.
94V Valla, T., Pervan, P., Milun, M.: Surf. Sci. 307-309 (1994) 843.
94W Wu, S. C., Garrison, K., Begley, A. M., Jona, F., Johnson, P. D.: Phys. Rev. B 49 (1994)
14081.
95H Hüfner, S.: Photoelectron Spectroscopy - Principles and Applications, Vol. 82 of Springer
Series in Solid-State Sciences, Springer, Berlin-Heidelberg, 1995.
95I Irmer, N., Frentzen, F., David, R., Stoppmanns, P., Schmiedeskamp, B., Heinzmann, U.: Surf.
Sci. 331-333 (1995) 1147.
95K Kang, J. S., Hwang, D. W., Hong, J. H., Jeong, J. I., An, H. K., Lee, Y. P., Lee, J. J., Kim, K.
H.: J. Magn. Magn. Mater. 150 (1995) 323.
95L Lo, W. S., Chien, T.-S., Fang, B.-S.: Phys. Rev. B 51 (1995) 14749.
95M Moulder, J. F., Stickle, W. F., Sobol, P. E., King Jr., R. C.: Handbook of X-ray Photoelectron
Spectroscopy, Physical Electronics, Inc., Eden Prairie 1995.
95P Peric, B., Valla, T., Milun, M., Pervan, P.: Vacuum 46 (1995) 1181.
95S Stampfl, A. P., Martin, R., Gardner, P., Bradshaw, A. M.: Phys. Rev. B 51 (1995) 10197.
96B Bei der Kellen, S., Freeman, A. J.: Phys. Rev. B 54 (1996) 11187.
96I Irmer, N., Frentzen, F., Yu, S. W., Schmiedeskamp, B., Heinzmann, U.: J. Electron Spectrosc.
Relat. Phenom. 78 (1996) 321.
96K Kaurila, T., Väyrynen, J., Isokallio, M.: J. Electron Spectrosc. Relat. Phenom. 78 (1996) 71.
96O Ollonqvist, T. E., Vayrynen, I. J., Dmitrieva, O. G., Artamonov, O. M.: Surf. Sci. 352-354
(1996) 693.
96P1 Pervan, P., Valla, T., Milun, M., Hayden, A. B., Woodruff, P. D.: J. Phys.: Condens. Matter 8
(1996) 4195.
96P2 Park, K. T., Simmons, G. W., Klier, K.: Surf. Sci. 367 (1996) 307.
96R Riffe, D. M., Hale, W., Kim, B., Erskine, J. L.: Phys. Rev. B 54 (1996) 17118.
96W Waldfried, C., McIlroy, D. N., Zhang, J., Dowben, P. A., Katrich, G. A., Plummer, E. W.: Surf.
Sci. 363 (1996) 296.
96Z1 Zacchigna, M., Astaldi, C., Prince, K. C., Sastry, M., Comicioli, C., Rosei, R., Quaresima, C.,
Ottaviani, C., Crotti, C., Antonini, A., Matteucci, M., Perfetti, P.: Surf. Sci. 347 (1996) 53.
96Z2 Zacchigna, M., Astaldi, C., Prince, K. C., Sastry, M., Comicioli, C., Evans, M., Rosei, R.,
Quaresima, C., Ottaviani, C., Crotti, C., Matteucci, M., Perfetti, P.: Phys. Rev. B 54 (1996)
7713.
97K Kang, J.-S., Hwang, D. W., Olson, C. G., Youn, S. J., Kang, K.-C., Min, B. I.: Phys. Rev. B 56
(1997) 10605.
97S Strisland, F., Raaen, S., Ramstad, A., Berg, C.: Phys. Rev. B 55 (1997) 1391.
97T Tao, H.-S., Madey, T. E., Rowe, J. W., Wertheim, G. K.: Phys. Rev. B 56 (1997) 6982.
98F1 Feydt, J., Elbe, A., Engelhard, H., Meister, G., Jung, Ch., Goldmann, A.: Phys. Rev. B 58
(1998) 14007.
98F2 Fang, B. S., Ballentine, C. A., Erskine, J. L.: Phys. Rev. B 58 (1998) 4299.
98H Haas, H., Wang, C. Z., Fähnle, M., Elsässer, C., Ho, K. M.: Phys. Rev. B 57 (1998) 1461.
98N Nahm, T.-U., Jung, R., Kim, J.-Y., Park, W. G., Oh, S. J., Park, J. H., Allen, J. W., Chung, S.
M., Lee, Y. S., Whang, C. N.: Phys. Rev. B 58 (1998) 9817.
99B Böttcher, A., Niehus, H.: Phys. Rev. B 60 (1999) 14396.
99L Len, P. M., Denlinger, J. D., Rotenberg, E., Kevan, S. D., Tonner, B. P., Chen, Y., Van Hove,
M. A., Fadley, C. S.: Phys. Rev. B 59 (1999) 5857.
00B1 Baraldi, A., Lizzit, S., Comelli, G., Goldoni, A., Hofmann, P., Paolucci, G.: Phys. Rev. B 61
(2000) 4534.
00B2 Barnes, C. J., Gleeson, M., Sahrakorpi, S., Lindroos, M.: Surf. Sci. 447 (2000) 165.
00G Grad, G. B., Blaha, P., Luitz, J., Schwarz, K.: Phys. Rev. B 62 (2000) 12743.
00K1 Kröger, J., Greber, T., Osterwalder, J.: Phys. Rev. B 61 (2000) 14146.
00K2 Kröger, J., Greber, T., Osterwalder, J.: Surf. Sci. 459 (2000) 173.
00L Legoas, S. B., Aranjo, A. A., Laks, B., Klautau, A. B., Frota-Pessoa, S.: Phys. Rev. B 61
(2000) 10417.
00R Ramstad, A., Strisland, F., Ramsvik, T., Borg, A.: Surf. Sci. 458 (2000) 135.
00S Surnev, S., Sock, M., Ramsey, M. G., Netzer, F. P., Wiklund, M., Borg, M., Andersen, J. N.:
Surf. Sci. 470 (2000) 171.
00T1 Theileis, V., Bross, H.: Phys. Rev. B 62 (2000) 13338.
00T2 Thomann, U., Reuß, Ch., Fauster, T., Passek, F., Donath, M.: Phys. Rev. B 61 (2000) 16163.
01A Abrikosov, I. A., Olovsson, W., Johansson, B.: Phys. Rev. Lett. 87 (2001) 176403.
01B Baraldi, A., Lizzit, S., Comelli, G., Paolucci, G.: Phys. Rev. B 63 (2001) 115410.
01G Ganduglia-Pirovano, M. V., Scheffler, M., Baraldi, A., Lizzit, S., Comelli, G., Paolucci, G.,
Rosei, R.: Phys. Rev. B 63 (2001) 205415.
01J Jeong, H.-K., Komesu, T., Yakovkin, I. N., Dowben, P. A.: Surf. Sci. 494 (2001) L773.
01K1 Krasovskii, E. E., Schattke, W.: Phys. Rev. B 63 (2001) 235112.
01K2 Kildemo, M., Ramsvik, T., Raaen, S.: Surf. Sci. 490 (2001) 1.
01L Lizzit, S., Baraldi, A., Groso, A., Reuter, K., Ganduglia-Pirovano, M. V., Stampfl, C.,
Scheffler, M., Stichler, M., Keller, C., Wurth, W., Menzel, D.: Phys. Rev. B 63 (2001) 205419.
01R Rader, O., Shikin, A. M.: Phys. Rev. B 64 (2001) 201406.
01S Shikin, A. M., Vyalikh, D. V., Prudnikova, G. V., Adamchuk, V. K.: Surf. Sci. 487 (2001) 135.
01W Wieling, S., Moldtsov, S. L., Gantz, Th., Laubschat, C.: Phys. Rev. B 64 (2001) 125424.
01Y Yakovkin, I. N., Zhang, J., Dowben, P. A.: Phys. Rev. B 63 (2001) 115408.
02B Bürgener, M., Berge, K., Gerlach, A., Meister, G., Goldmann, A.: to be published.
02J Janin, E., von Schenk, H., Helldén, S., Tjernberg, O., Karlsson, U. O., Göthehild, M.: Surf. Sci.
515 (2002) 462.
02R1 Raj, S., Padhi, H. C., Palit, P., Basa, D. K., Polasik, M., Pawlowski, F.: Phys. Rev. B 65 (2002)
193105.
02R2 Radosavkic, D., Barrett, N., Belkhou, R., Marsot, N., Guillot, C.: Surf. Sci. 516 (2002) 56.
115116.

(A. Goldmann (Auth.), A. Goldmann (Eds.) ) Noble Me PDF

Hochgeladen von

Dokumentinformationen

Originaltitel

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

(A. Goldmann (Auth.), A. Goldmann (Eds.) ) Noble Me PDF

Hochgeladen von

Copyright:

Verfügbare Formate

Ref. p. 12] 1.

1.1 Historical remarks

1.2 Arrangement of data

1.3 Definition of quantities

Fig. 1. Schematics of photoemission (top) and inverse photoemission

I(Ek, !ω) ≈ ∑ ∫ d3k |〈f | p | i〉|2 · δ1 . δ2 (1)

I (Ek, !ω) ≈ ∑ ∫ d3k · δ1 . δ2 (2)

Fig. 3. Illustration of the fact that in angle-integrated

Table 1. Commonly used line sources for photoelectron spectroscopy [78C1].

Source Energy Relative Typical intensity at Linewidth

He I 21.22 100 1 ⋅ 1012 3

Photoelectron spectroscopies and related or complementary techniques are looking through a

Fig. 6. fcc(111). (Bottom) BBZ and (top) SBZ showing

Fig. 7. bcc(100). (Bottom) BBZ and (top) SBZ

Fig. 10. hcp(0001). (Bottom) BBZ and (top) SBZ

Fig. 11. hcp(1010). (Bottom) BBZ and (top) SBZ

1.4 Frequently used symbols

Symbol Unit Property

1.5 List of abbreviations

APS appearance potential spectroscopy

1.6 References for 1

1887H Hertz, H.: Ann. Physik (Wiedemann's) 31 (1887) 983.

2.9 Noble metals

All data refer to room-temperature samples unless stated differently.

2.9.2 Cu (Copper) (Z = 29)

Lattice: fcc, a = 3.61 Å [63W].

Table 1. Cu. Core-level binding energies in eV

For core-hole lifetime broadenings see [92F].

Γ8+(12) –2.80 –2.75 –2.85 –2.79 –2.85(10)1) –2.73

X7+(5) –2.00 –2.05 –2.05 –1.95 –2.032,3) –2.01

1) [89W1]. 2) [83W]. 3) [79H1].

L6– (2') –0.39 –0.9(1) 3), –0.85 5)

1) [78D2]. 2) [79D]. 3) [79K2]. 4) [79T]. 5) [82L]. 6) [84C].

Γ(2') 23.3 24.2 23.8 23.7(5) 1) *)

L(1) 3.94 4.1 3.8 4.1 2)

X6– (4') 2.03 2.02 2.21 2.3(3) 4)

*) Data taken from a figure. See also [01S1].

Figures for 2.9.2

Fig. 2. Cu. Overview XPS spectrum.

Fig. 3. Cu. XPS data showing the

Fig. 6. Cu. Photoelectron spectra obtained from

DOS [states / eV⋅atom]

2 Fig. 16. Cu. Calculated ε2 spectrum (solid line) in

Initial state energy E i [eV]

6+(3) 6(3) 7 + 7+ experimental data for the occupied

Fig. 22. Cu, Ag. Experimental upper

15 7-(5’) Fig. 23. Cu. Compilation of

Fig. 29. Cu(100). Two examples showing angle-

Fig. 34. Cu(100). Photoelectron

T = 70 K Fig. 36. Cu(100). Temperature-dependent spectra for

Fig. 35. Cu(100). Temperature dependence of normal-

For Fig. 39 see next page

Cu(100) Cu(100) α = −20°

Γ XUL Γ XWK Fig. 42. Cu(100). E(k||) diagram for

4 generally shown as solid symbols

For Fig. 45 see next page

Fig. 44. Cu(110). Normal-emission

7 induced by a weak satellite line of the

Temp.coeff. b [10− 4 K −1]

−8 −6 −4 −2 0 = EF 0° 20° 40° 60°

1.4 0.012 Λ1 lower

Pfi /2m [Ry]

Fig. 55. Cu(111). Normal-emission photoelectron