The molecular mean-field approach for correlated relativistic calculations

A new approach for relativistic correlated electron structure calculations is proposed by which a transformation to a two-spinor basis is carried out after solving the four-component relativistic Hartree-Fock equations. The method is shown to be more accurate than approaches that apply an a priori transformation to a two-spinor basis. We also demonstrate how the two-component relativistic calculations with properly transformed two-electron interaction can be simulated at the four-component level by projection techniques, thus allowing an assessment of errors introduced by more approximate schemes. © 2009 American Institute of Physics.