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Ab initio effective core potentials for molecular calculations. Potentials for main group elements Na to Bi
A consistent set of ab initio effective core potentials (ECP) has been generated for the main group elements from Na to Bi using the procedure originally developed by Kahn. The ECP's are derived from ...

Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg

J. Chem. Phys. 82, 270 (1985); doi:10.1063/1.448799

Issue Date: 1 January 1985

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P. Jeffrey Hay and Willard R. Wadt
Theoretical Division, MS J569, Los Alamos National Laboratory, Los Alamos, New Mexico 87545
Ab initio effective core potentials (ECP's) have been generated to replace the Coulomb, exchange, and core-orthogonality effects of the chemically inert core electron in the transition metal atoms Sc to Hg. For the second and third transition series relative ECP's have been generated which also incorporate the mass–velocity and Darwin relativistic effects into the potential. The ab initio ECP's should facilitate valence electron calculations on molecules containing transition-metal atoms with accuracies approaching all-electron calculations at a fraction of the computational cost. Analytic fits to the potentials are presented for use in multicenter integral evaluation. Gaussian orbital valence basis sets are developed for the (3d,4s,4p), (4d,5s,5p), and (5d,6s,6p) orbitals of the first, second, and third transition series atoms, respectively. All-electron and valence-electron atomic excitation energies are also compared for the low-lying states of Sc–Hg, and the valence-electron calculations are found to reproduce the all-electron excitation energies (typically within a few tenths of an eV). The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 29 December 1983; accepted 26 September 1984
Permalink: http://link.aip.org/link/?JCPSA6/82/270/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.20.Ej
    Electronic structure of atoms and molecules: theory Specific calculations and results Ab initio LCAO and SCF calculations
  • 31.20.Rx
    Electronic structure of atoms and molecules: theory Specific calculations and results Valence bond calculations (ab initio or not); spin density and electron density calculations
  • YEAR: 1985

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
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REFERENCES (30)
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