Relativistic energy‐consistent pseudopotentials—Recent developments

Abstract

The direct adjustment of two‐component pseudopotentials (scalar‐relativistic + spin‐orbit potentials), to atomic total energy valence spectra derived from four‐component multiconfiguration Dirac–Hartree–Fock all‐electron calculations based on the Dirac–Coulomb–Breit Hamiltonian, has been made a routine tool for an efficient treatment of heavy main‐group elements. Both large‐core (nsp valence shell) and small‐core ((n − 1)spd nsp valence shell) potentials have been generated for all the post‐d elements of groups 13–17. At the example of lead and bismuth compounds (PbHal, BiH, BiO, BiHal (Hal = F, Cl, Br, I)), we show how small‐core and large‐core potentials can be combined in accurate, yet computationally economic, spin‐free‐state‐shifted relativistic electronic structure calculations of molecular ground and excited states. © 2002 Wiley Periodicals, Inc. J Comput Chem 23: 767–778, 2002