Theory of Auger spectra for molecular-field-split core levels.

Abstract

A theory for nonradiative decay of molecular-field-split states is presented. It is shown that the relative inner-shell sublevel cross sections for Auger transitions are sensitively dependent on the matching of spin-orbit and molecular-field interactions. This can lead to suppression of particular sublevel Auger transitions and to a breakdown of the constant core-hole lifetime approximation. The investigated effects are caused by a strong dependence of the Auger intensity on the mutual local space orientation of initial- and final-state orbitals. These features are illustrated for S 2p (${\mathit{L}}_{\mathrm{I}\mathrm{I},\mathrm{I}\mathrm{I}\mathrm{I}}$VV) Auger spectra of ${\mathrm{H}}_{2}$S, and explain the apparent mismatch of 2p spin-orbit energies observed in Auger and photoelectron spectra of this molecule. \textcopyright{} 1996 The American Physical Society.