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Relativistic energy‐consistent pseudopotentials—Recent developments
Author(s) -
Stoll Hermann,
Metz Bernhard,
Dolg Michael
Publication year - 2002
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.10037
Subject(s) - hamiltonian (control theory) , relativistic quantum chemistry , valence (chemistry) , excited state , atomic physics , valence electron , physics , bismuth , core electron , chemistry , electron , quantum mechanics , mathematical optimization , mathematics , organic chemistry
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