Valence and core photoelectron spectroscopies

The roots of core and valence level photoemission can be tracked back to the famous article of Einstein explaining the photoelectric effect.164 In this work, he postulated the quantum hypothesis for absorption of radiation by the fundamental equation  

Much effort has focused on the interpretation of core level energies, or, alternatively on core level shifts with respect to well-defined references.165,167 A core-level energy difference or shift is fundamentally a difference in energy between the final states of the photoemission process, that is, the energy difference between electronic states in presence of the core-hole left by the absorption of radiation. A typical task for analysis 

213 occurs with the involvement of the rather free valence electrons of the metal and thus provides information about them. In the case of nanosized systems, it is clear that the mobility of such valence electrons is related to size by quantum confinement effects. On the other hand, such a skewing of the XPS line shape is generally known as the Doniach-Sunjic line shape and must be corrected for in order to obtain accurate values of the core-level binding energy.  

XPS is routinely employed for supported metal catalysts and results reported in numerous papers each year. However, the vast m ority of these studies are conducted at low pressure (below 10 Torr). The 

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Magic Number Carbon Clusters Ionization Potentials and Selective Reactivity. D. L. Lichtenberger, K. W. Nebesny, C. D. Ray, D. R. Huffman, and L. D. Lamb, Chem. Phys. Lett., 176, 203 (1991). Valence and Core Photoelectron Spectroscopy of C o, Buckrainsterfullerene. 

The simplest, and perhaps the most important, information derived from photoelectron spectra is the ionization energies for valence and core electrons. Before the development of photoelectron spectroscopy very few of these were known, especially for polyatomic molecules. For core electrons ionization energies were previously unobtainable and illustrate the extent to which core orbitals differ from the pure atomic orbitals pictured in simple valence theory. 

It is commonly accepted that chemisorption of CO on transition metals takes place in a way that is quite similar to bond formation in metal carbonyls (4). First experimental evidence for this assumption was obtained from a comparison of the C—O stretching frequencies (5) and was later confirmed by data on the bond strength (6) as well as by valence and core level ionization potentials obtained by photoelectron spectroscopy (7). Recent investigations have in fact shown that polynuclear carbonyl compounds with more than about 3-4 metal atoms exhibit electronic properties that are practically identical to those of corresponding CO chemisorption systems (8, 9), thus supporting the idea that the bond is relatively strongly localized to a small number of metal atoms forming the chemisorption site. 

Photoelectron spectroscopy of valence and core electrons in solids has been useful in the study of the surface properties of transition metals and other solid-phase materials. When photoelectron spectroscopy is performed on a solid sample, an additional step that must be considered is the escape of the resultant photoelectron from the bulk. The analysis can only be performed as deep as the electrons can escape from the bulk and then be detected. The escape depth is dependent upon the inelastic mean free path of the electrons, determined by electron-electron and electron-phonon collisions, which varies with photoelectron kinetic energy. The depth that can be probed is on the order of about 5-50 A, which makes this spectroscopy actually a surface-sensitive technique rather than a probe of the bulk properties of a material. Because photoelectron spectroscopy only probes such a thin layer, analysis of bulk materials, absorbed molecules, or thin films must be performed in ultrahigh vacuum (<10 torr) to prevent interference from contaminants that may adhere to the surface. 

X-ray photoelectron spectroscopy (XPS) is among the most frequently used surface chemical characterization teclmiques. Several excellent books on XPS are available [1, 2, 3, 4, 5, 6 and 7], XPS is based on the photoelectric effect an atom absorbs a photon of energy hv from an x-ray source next, a core or valence electron with bindmg energy is ejected with kinetic energy (figure Bl.25.1) ... 

Several UHV techniques which have been developed have not found such wide use in corrosion analysis, despite potential applicability. Ultraviolet photoelectron spectroscopy (UPS) is one of these, operating in a similar fashion to XPS (but using an ultraviolet excitation), and probing the valence electrons, rather than the core electrons of the atoms. Because the energies of the valence electrons are so very sensitive to the precise state of the atom, the technique is in principle very informative however exactly this high sensitivity renders the data difficult to interpret, particularly as a routine... 

The nature of the final state depends upon the energy, hv, of the exciting photons. In X-ray photoelectron spectroscopy (XPS) the exciting photons are provided by sources such as A1 Ka (1,486 eV) or Mg Ka (1,253 eV) and excitation of the core electrons of the molecules is observed. In UV photoelectron spectroscopy (UPS), Hel (21.2eV) or Hell (40.8 eV) radiation is used and excitation from the valence region of the neutral molecule is observed. XPS and UPS are surface-sensitive techniques, which are capable of providing extremely useful information on the chemical nature of a surface or interface and, in the case of the XPS, the conformational state of the molecules at the surface [64]. 

Photoelectron spectroscopy involves detection and analysis of the photoelectrons produced by interaction of radiation with a solid. This radiation may be X-rays (for X-ray photoelectron spectroscopy, XPS or ESCA) or ultraviolet radiation (UPS) it causes the removal of a single core or valence electron, respectively. The kinetic energy, Ek, of these electrons is given by the following equation ... 

ESCA involves the measurement of binding energies of electrons ejected by interactions of a molecule with a monoenergetic beam of soft X-rays. For a variety of reasons the most commonly employed X-ray sources are Al and MgKol>2 with corresponding photon energies of 1486.6 eV and 1253.7 eV respectively. In principle all electrons, from the core to the valence levels can be studied and in this respect the technique differs from UV photoelectron spectroscopy (UPS) in which only the lower energy valence levels can be studied. The basic processes involved in ESCA are shown in Fig. 1. 

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