Molecular Spin–Orbit Coupling Constants. The Role of Core Polarization

Abstract

The ab initio computation of molecular spin–orbit coupling constants from Hartree–Fock wavefunctions is extended to second-row nonhydride diatomic molecules, with only the smallest integrals treated approximately. Agreement with experiment is good (∼5%), providing core polarization effects are included. The extension to polyatomic molecules seems possible since reasonable values are obtained even from minimal basis set wavefunctions, and the contributions from two-center integrals are self-canceling.