The valence state of sulphur in sulphoxides: the role of 3d-orbitals

Abstract

A number of electron configurations describing the valence state of sulphur in sulphoxides have been investigated by an approach which neglects interatomic exchange terms. Energies were derived by treating variationally the parameters which define the size and orientation of the valence orbitals. The results are in favour of a valence description of sulphur based on V₄[s²p³d′], V₃⁺[s²p³], and V₄[s²p³d″] where the d-orbitals are expected to participate also in σ-bonding with oxygen and carbon atoms. The effect of interatomic exchange terms is discussed.