Theoretical investigation on the acceptor role of [formula omitted] MOs in three and four-membered ring thio compounds and their open chain analogues. Comparison of ground state, lowest energy triplet state and anion properties

Abstract

Ab initio SCF-CI (6-31G ∗∗/MP2 and 6-31G ∗∗/MP4) computation of the singlet ground state, lowest energy triplet and anion states have been carried out for a series of divalent sulfur compounds. The aim of this study was to provide an insight into the acceptor capacity of σ ∗ MOs involved in the temporary states created in X-ray photoabsorption and electron transmission spectroscopies. A roughly parallel behavior is observed between triplet and anion species, either for vertical (GS geometry) or relaxed moieties. Qualitative correlations are presented between the calculated energies and molecular properties such as the CS bond length or the energy of the first virtual σ ∗ MO.