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

Journal of Chemical Physics - Tập 82 Số 1 - Trang 270-283 - 1985
P. Jeffrey Hay1, Willard R. Wadt1
1Theoretical Division, MS J569, Los Alamos National Laboratory, Los Alamos, New Mexico 87545

Tóm tắt

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).

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Journal of Chemical Physics

Tập 82 Số 1

270-283

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