Perturbation Theory Treatment of Spin-Orbit Coupling II: A Coupled Perturbed Kohn-Sham Method.

Abstract

A noncanonical coupled perturbed Kohn-Sham density functional theory (KS-DFT)/Hartree-Fock (HF) treatment of spin-orbit coupling (SOC) is provided. We take the scalar-relativistic KS-DFT/HF solution, obtained with a relativistic effective core potential, as the zeroth-order approximation. Explicit expressions are given for the total energy through the 4th order, which satisfy the 2n + 1 rule. Second-order expressions are provided for orbital energies and density variables of spin-current DFT. Test calculations are carried out on the halogen homonuclear diatomic and hydride molecules, including 6p and 7p elements, as well as open-shell negative ions. The computed properties through second or third order match well with those from reference two-component self-consistent field calculations for total and orbital energies as well as spin-current densities. In only one case (At2-) did a significant deviation occur for the remaining density variables. Our coupled perturbation theory approach provides an efficient way of adding the effect of SOC to a scalar-relativistic single-reference KS-DFT/HF treatment, in particular because it does not require diagonalization in the two-component spinor basis, leading to saving factors on the number of required floating-point operations that may exceed one order of magnitude.