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By G.A. Somorjai, M.A. van Hove

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However, in some cases comparison with experimental EXAFS data from bulk material can help in circumventing the phase shift uncertainty: essentially the bulk and surface phase shifts are assumed equal and these then divide out in the ratio of the surface to bulk data. A drawback of SEXAFS is that synchrotron radiation is needed as a source of X-rays. 1 UPS and XPS (Ultraviolet and X-Ray Photoernission Spectroscopy) and AR UPS (Angle-Resolved UPS) Photon-induced emission of electrons is an obvious tool for structural analysis in two ways.

This relation only rarely fits the experiment, however, because the charge distribution at surfaces is governed by more complicated processes than polarizability, such as charge transfer between substrate and adsorbate. Thus, there are examples of sign reversal of the work function change as coverage varies, while there is no detectable change in adsorption geometry (cf. Sect. VI). Nevertheless, general systematic observations are quite helpful. For example, the sign of the work function change for atomic adsorption is mostly that implied by the sign of the valency of the adsorbates, as one would expect; furthermore, in atomic adsorption it appears that large atoms (such as alkali atoms) produce large work function changes, mainly because of the size effect.

The depth of penetration affects peak widths markedly: the shallower the penetration, the broader is the diffraction peak. By simulating such I-V curves numerically with the help of a suitable theory, it is often possible to determine the relative positions of surface atoms (including therefore bond lengths and bond angles)2a'O; it may also be possible to indicate roughly the thermal vibration state of surface atoms 2a). However, a chemical identification of the surface atoms is not possible with LEED.

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