Photoelectron spectroscopy of localized levels near surfaces: Scattering effects and relaxation shifts

Abstract

We calculate the spectrum of photoelectrons excited from localized levels in solids far into the continuum (XPS situation), in a model that takes into account exactly their interaction with a boson-like spatially non-uniform field. The general results are applied to discuss the spectra of photoelectrons in metals, where the dominant interaction is the coupling to bulk and surface plasmons. In particular, we study the modification of spectral sum rules connecting the strength of inelastic processes with the energy shifts in the spectrum, showing that the electron (“extrinsic”) scattering changes the average position of the spectrum with respect to the pure “intrinsic” result in the “sudden approximation”, which leads also to its dependence on the excitation energy and position of localized level. We estimate these deviations in a simple model which nevertheless reproduces correctly the dynamical aspects of the problem.