A Valence-Bond Study of the Role of 3d Orbitals in the Bonding in ClF₃

Abstract

Minimal basis set valence-bond calculations on ClF₃, with, and without, the use of chlorine 3d orbitals are described. The most important structure is a spin-paired diradical structure. The covalent structure with three covalent Cl -F covalent bonds has a sufficiently low importance that 3d orbitals are not essential for describing the bonding in ClF₃. Chlorine 3d orbitals do have a significant contribution to the calculated energy.