Theoretical investigation of the sulphur K-LL auger energies and chemical shifts in a series of sulphur compounds

Abstract

Two series of investigations are reported on LL double-hole states of molecules containing sulphur. First the results on the LL double ionization potentials and K-LL Auger energies of H 2S and SO 2 show that the use of a frozen-orbital approximation is preferable to SCF methods for calculation of chemical shifts in K-LL Auger energies and LL ionization potentials. Secondly chemical shifts of K-LL Auger energies of a series of model molecules H 2S, H 2SO 4, H 4SO 2 and H 2SO 2 are correlated with the formal oxidation state of sulphur. This correlation gives a shift of 12 eV in Auger energy per formal charge on sulphur.