Analytic evaluation of first-order properties within the mean-field variant of spin-free exact two-component theory.

2019

We present a scheme for the calculation of energies and analytic energy gradients within spin-free exact two-component (SFX2C) theory in its mean-field variant, which we refer to as SFX2C-mf. In the presented scheme, the Foldy-Wouthuysen transformation is carried out after the spin-free four-component Hartree-Fock treatment such that in electron-correlated calculations only the non-mean-field part of the two-electron interactions is handled in an untransformed manner. The formulation of analytic gradients requires some adjustments in comparison with the nonrelativistic case, i.e., the additional solution of the spin-free Dirac Coulomb coupled-perturbed Hartee-Fock equations together with a …