Nonradiative and dissociative decay channels of core-excited H2S studied by ab initio calculations

Ab initio studies of the 2p(3a1)-6a1 and 2p(3a1)-3b2 photoexcitation resonances of H2S have been carried out in order to support interpretations of recent photoelectron and autoionization spectra using synchrotron-radiation excitation. The full H2S*S+H2 and H2S*S+H+H potential-energy surfaces as well as the resonant energies for autoionization (Auger) decay of core-excited states in the fragment HS species have been obtained by multiconfiguration self-consistent-field calculations. The results support an interpretation of the spectral fundings in terms of fast dissociation of the H2S* 2p-16a11 and 2p-13b21 states to core-excited states in HS* followed by resonance Auger decay to HS+ valence single-hole states.