All-electron relativistic calculations on AgH. An investigation of the Cowan-Griffin operator in a molecular species

Journal Article · Thu Mar 03 04:00:00 EST 1983 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100228a012· OSTI ID:5485986

Martin, R L

The Cowan-Griffin relativistic operator, which retains only the mass-velocity and one-electron Darwin terms of the Breit-Pauli Hamiltonian, has been shown to provide a remarkably good approximation to the more sophisticated Dirac-Hartree-Fock (DHF) approach for many atomic systems. In this paper, the result of applying the Cowan-Griffin operator in first order to a nonrelativistic self-consistent-field (SCF) wave function expanded in a basis of Gaussian functions is reported for Ag and AgH. Comparisons are made with previously reported numerical wave functions for Ag and with the recent Slater-type-orbital expansion of the DHF wave function for AgH reported by Lee and McLean. The results of the present method are in excellent agreement with the DHF work and suggest that the approach might provide an attractive alternative to the DHF approximation. Further support for the contention of Ziegler, Snijders, and Baerends that the relativistic bond length contraction in AgH is caused by the mass-velocity term, as opposed to an atomic orbital contraction, is also presented.

• Research Organization: Los Alamos National Lab., NM
• OSTI ID: 5485986
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Journal Issue: 5 Vol. 87:5; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BOND LENGTHS
CALCULATION METHODS
DIMENSIONS
ELECTRONIC STRUCTURE
ELEMENTS
HYDRIDES
HYDROGEN COMPOUNDS
LENGTH
METALS
MOLECULAR STRUCTURE
PERTURBATION THEORY
SILVER
SILVER COMPOUNDS
SILVER HYDRIDES
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS