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

Journal Article · Tue Jan 01 04:00:00 EST 1985 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.448799· OSTI ID:5987190

Hay, P J; Wadt, W R

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).

• Research Organization: Theoretical Division, MS J569, Los Alamos National Laboratory, Los Alamos, New Mexico 87545
• OSTI ID: 5987190
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 82:1; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640305* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Theory-- (-1987)
74 ATOMIC AND MOLECULAR PHYSICS
ELECTRONIC STRUCTURE
ELECTRONS
ELEMENTARY PARTICLES
ELEMENTS
FERMIONS
FUNCTIONS
LEPTONS
METALS
POTENTIALS
TRANSITION ELEMENTS
VALENCE
WAVE FUNCTIONS