HIGH-RESOLUTION PHOTOELECTRON-SPECTROSCOPY OF SULFUR 2P ELECTRONS IN H2S, SO2, CS2, AND OCS

High-resolution photoelectron spectra for the 2p electrons in H2S, SO2 , CS2, and OCS show the effects of vibrational excitation in the core- excited species as well as the splitting of the 2p(3/2) hole state by the molecular field. Theoretical calculations at the Hartree-Fock leve l account reasonably well for the vibrational structure. The molecular -field splitting is calculated with a configuration interaction-based method using large basis sets. This produces values for the 2p(3/2) sp litting of 108, 96, 129, and 144 meV for the title molecules, to be co mpared with experimental values of 110, 105, 140, and 150 meV. Thus al l observed features in the spectra are quantitatively accounted for by theoretical modeling. (C) 1996 American Institute of Physics.