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Four‐component relativistic Kohn–Sham theory
Author(s) -
Saue Trond,
Helgaker Trygve
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.10066
Subject(s) - kohn–sham equations , hamiltonian (control theory) , physics , anharmonicity , parametrization (atmospheric modeling) , density functional theory , relativistic quantum chemistry , coulomb , quantum mechanics , component (thermodynamics) , operator (biology) , chemistry , mathematics , mathematical optimization , radiative transfer , electron , biochemistry , repressor , transcription factor , gene
A four‐component relativistic implementation of Kohn–Sham theory for molecular systems is presented. The implementation is based on a nonredundant exponential parametrization of the Kohn–Sham energy, well suited to studies of molecular static and dynamic properties as well as of total electronic energies. Calculations are presented of the bond lengths and the harmonic and anharmonic vibrational frequencies of Au 2 , Hg 2+ 2 , HgAu + , HgPt, and AuH. All calculations are based on the full four‐component Dirac–Coulomb Hamiltonian, employing nonrelativistic local, gradient‐corrected, and hybrid density functionals. The relevance of the Coulomb and Breit operators for the construction of relativistic functionals is discussed; it is argued that, at the relativistic level of density‐functional theory and in the absence of a vector potential, the neglect of current functionals follows from the neglect of the Breit operator. © 2002 Wiley Periodicals, Inc. J Comput Chem 23: 814–823, 2002