Abstract
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.
Keywords
Core electronPhysicsValence (chemistry)Atomic orbitalRelativistic quantum chemistryAtomic physicsPauli exclusion principleCore chargeElectronValence electronAb initioQuantum mechanics
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Publication Info
- Year
- 1978
- Type
- article
- Volume
- 68
- Issue
- 5
- Pages
- 2386-2397
- Citations
- 120
- Access
- Closed
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Cite This
Luis R. Kahn,
P. Jeffrey Hay,
Robert D. Cowan
(1978).
Relativistic effects in <i>a</i> <i>b</i> <i>i</i> <i>n</i> <i>i</i> <i>t</i> <i>i</i> <i>o</i> effective core potentials for molecular calculations. Applications to the uranium atom.
The Journal of Chemical Physics
, 68
(5)
, 2386-2397.
https://doi.org/10.1063/1.436009
Identifiers
- DOI
- 10.1063/1.436009