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The molecular mean-field approach for correlated relativistic calculations

2009; American Institute of Physics; Volume: 131; Issue: 12 Linguagem: Inglês

10.1063/1.3239505

1520-9032

Jetze Sikkema, Lucas Visscher, Trond Saue, Miroslav Iliaš,

Chemical Thermodynamics and Molecular Structure

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.