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Ground‐state properties of MH, MCl, and M 2 (M=Cu, Ag, and Au) calculated by a scalar relativistic density functional theory
Author(s) -
Suzumura Toshihisa,
Nakajima Takahito,
Hirao Kimihiko
Publication year - 1999
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1999)75:4/5<757::aid-qua42>3.0.co;2-r
Subject(s) - relativistic quantum chemistry , bond dissociation energy , density functional theory , theory of relativity , chemistry , ground state , dissociation (chemistry) , dipole , physics , atomic physics , bond length , scalar (mathematics) , hamiltonian (control theory) , quantum mechanics , molecule , geometry , mathematical optimization , mathematics
The effects of relativity on the bond lengths, vibrational frequencies, dissociation energies, and dipole moments of the ground states of the group IB hydrides MH, chlorides MCl, and dimers M 2 (M=Cu, Ag, and Au) have been studied by relativistic density functional theory (DFT) with the B88 plus one‐parameter progressive (BOP) exchange–correlation functional. The relativistic effects were included through a scalar relativistic scheme by the elimination of the small components (RESC) of the four‐component Dirac spinors. Comparisons were made between all‐electron results using the nonrelativistic Hamiltonian, results with quasi‐relativistic effective core potentials (ECP), and results with a spin‐free RESC scheme. The RESC approach clearly works very well. The bond distances, vibrational frequencies, and dissociation energies show a good agreement with the experiment. The expected trends of bond length decrease, harmonic vibrational frequency increase, and dipole moment decrease with relativity are found. Although the dissociation energy increases with the relativity for hydrides and dimers, the reverse trend is observed for chlorides. A quasi‐relativistic ECP also works well for hydrides. However, ECP gives rather poor description for chlorides and dimers. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 75: 757–766, 1999