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.