Density-Corrected Density Functional Theory for Open Shells: How to Deal with Spin Contamination.

Abstract

Density functional theory (DFT) is usually used self-consistently to predict chemical properties, but the use of the Hartree-Fock (HF) density improves energetics in certain, well-characterized cases. Density-corrected (DC) DFT provides the theory behind this, but unrestricted Hartree-Fock (UHF) densities yield poor energetics in cases of strong spin contamination. Here we compare with restricted open-shell HF (ROHF) across 13 different functionals and two DC-DFT methods. For significant spin contamination, ROHF densities outperform UHF densities by as much as a factor of 3, depending on the energy functional, and ROHF-DFT improves over self-consistent DFT for most of the tested functionals. We refine the DC(HF)-DFT algorithm to use ROHF densities in cases of severe spin contamination.