Basis-set extensions for two-component spin–orbit treatments of heavy elements

Abstract

The accuracy of standard basis sets of quadruple-zeta and lower quality for the use in two-component self-consistent field procedures including spin–orbit coupling is investigated for the elements In–I and Au–At. Spin–orbit coupling leads to energetic and spatial splittings of inner shells, which are not described accurately with standard basis sets optimized for scalar relativistic calculations. This results in large errors in total atomic energies and significant errors in atomization energies of compounds containing these atoms. We show how these errors can be corrected by adding just a few steep sets of basis functions and demonstrate the quality of the resulting extended basis sets.