Relativistic effects in ab initio effective core potentials for molecular calculations. Applications to the uranium atom

Journal Article · Wed Mar 01 04:00:00 EST 1978 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.436009· OSTI ID:5202114

Kahn, L R; Hay, P J; Cowan, R D

The procedure of deriving ab initio effective core potentials (ECP) to incorporate the Coulomb and exchange effects as well as orthogonality constraints from the inner core electrons is extended to include the dominant relativistic effects on the valence orbitals. An ab initio approach is then described which enables the valence electrons in heavy atoms to be treated in a standard nonrelativistic manner by including the effect of the relativistic core-valence interactions directly into the ECP. The starting point for this procedure is the Pauli Hartree-Fock relativistic treatment of Cowan and Griffin. The pseudo-orbital transformation and derivation of the l-dependent effective core potentials are analogous to the nonrelativistic case with certain modifications. Analytic forms for the pseudo-orbitals and ECP's are derived for the U atom, and results of valence electron calculations are presented.

• Research Organization: Battelle Columbus Laboratories, Metal Science Section, Columbus, Ohio 43201
• OSTI ID: 5202114
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 68:5; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ACTINIDES
ELECTRONIC STRUCTURE
ELEMENTS
ENERGY LEVELS
FIELD THEORIES
FUNCTIONS
GENERAL RELATIVITY THEORY
GROUND STATES
METALS
RELATIVITY THEORY
URANIUM
WAVE FUNCTIONS