Improved ab initio effective potentials for Ar, Kr, and Xe with applications to their homonuclear dimers

Journal Article · Tue Dec 01 04:00:00 EST 1981 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.441941· OSTI ID:5945659

Christiansen, P A; Pitzer, K S; Lee, Y S; Yates, J H; Ermler, W C; Winter, N W

Effective core potentials for the Ar, Kr, and Xe atoms derived from numerical Hartree--Fock and Dirac--Hartree--Fock wave functions are applied in SCF and CI calculations of homonuclear diatomic potential energy curves. Detailed comparisons are made with the all-electron calculations of Wadt for the ground and lowest positive states. Relativistic effects, excluding spin--orbit coupling, are seen to be relatively unimportant. Plots of the potential energy curves and computed spectroscopic constants show excellent agreement with the all-electron results. On the other hand, comparisons with results obtained using effective potentials derived using varients of Phillips--Kleinman procedures show dramatic differences for Xe/sub 2/ and Xe/sub 2//sup +/. From SCF calculations on Xe/sub 2/ and Xe/sub 2//sup +/ it was found that the explicit inclusion of the spin--orbit operator in the SCF procedure (using ..omega..--..omega.. coupling) results in essentially the same potential curves obtained by adding the spin--orbit correction as a final semiempirical perturbation.

• Research Organization: Department of Chemistry and Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720
• OSTI ID: 5945659
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 75:11; 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
ARGON
CONFIGURATION INTERACTION
DIMERS
ELECTRONIC STRUCTURE
ELEMENTS
ENERGY
FLUIDS
GASES
HARTREE-FOCK METHOD
KRYPTON
NONMETALS
POTENTIAL ENERGY
RARE GASES
SELF-CONSISTENT FIELD
XENON