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

A theory for nonradiative decay of molecular-held-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 (L(II,III)VV) Auger spectra of H2S, and explain the apparent mismatch of 2p spin-orbit energies observed in Auger and photoelectron spectra of this molecule.