Variational Relativistic Two-Component Complete-Active-Space Self-Consistent Field Method

J Chem Theory Comput. 2019 May 14;15(5):2974-2982. doi: 10.1021/acs.jctc.9b00011. Epub 2019 May 2.

Abstract

The accurate description of the electronic structure of transition metals and their compounds can be complicated by both the large number of close-lying states that often have multiconfigurational nature and significant relativistic effects. In order to address these challenges we present a two-component complete-active-space self-consistent field method that includes scalar relativistic effects and one-electron spin-orbit coupling during the self-consistent wave function optimization procedure. These relativistic effects are included via an "exact two-component" transformation of the solution of the one-electron modified Dirac equation. The method is applied to the study of spin-orbit splitting of ground and low-lying excited states of main group elements and selected transition metals.