Relativistic all-electron two-component self-consistent density functional calculations including one-electron scalar and spin-orbit effects.

Abstract

We have implemented a Gaussian basis-set two-component self-consistent field method based on the fourth-order nuclear-only Douglas-Kroll-Hess approximation. Two-electron spin-orbit effects are included using Boettger's screened-nuclear spin-orbit approximation. In our two-component approach, the spin-orbit interaction is taken into account in a variational fashion employing a generalized Kohm-Sham scheme which allows one to work with hybrid density functionals. For open-shell systems we adopt the noncollinear spin-density approximation. Results are presented for equilibrium bond lengths, harmonic vibrational frequencies, and bond dissociation energies with local spin-density, generalized gradient approximation, and hybrid functionals in a set of benchmark molecules.