The ab initio model potential method. Second series transition metal elements

Journal Article · Mon Oct 15 04:00:00 EDT 1990 · Journal of Chemical Physics; (USA)

DOI:https://doi.org/10.1063/1.459580· OSTI ID:6313334

Barandiaran, Z; Seijo, L ^[1]; Huzinaga, S ^[2]

---

1. Departamento de Quimica Fisica Aplicada, C-14, Universidad Autonoma de Madrid, 28049 Madrid (Spain)
2. Department of Chemistry, The University of Alberta, Edmonton, Alberta T6G 2G2 (Canada)

The {ital ab} {ital initio} core method potential model (AIMP) has already been presented in its nonrelativistic version and applied to the main group and first series transition metal elements (J. Chem. Phys. {bold 86}, 2132 (1987); {bold 91}, 7011 (1989)). In this paper we extend the AIMP method to include relativistic effects within the Cowan--Griffin approximation and we present relativistic Zn-like core model potentials and valence basis sets, as well as their nonrelativistic Zn-like core and Kr-like core counterparts. The pilot molecular calculations on YO, TcO, AgO, and AgH reveal that the 4{ital p} orbital is indeed a core orbital only at the end part of the series, whereas the 4{ital s} orbital can be safely frozen from Y to Cd. The all-electron and model potential results agree in 0.01--0.02 A in {ital R}{sub {ital e}} and 25--50 cm{sup {minus}1} in {bar {nu}}{sub {ital e}} if the same type of valence part of the basis set is used. The comparison of the relativistic results on AgH with those of the all-electron Dirac--Fock calculations by Lee and McLean is satisfactory: the absolute value of {ital R}{sub {ital e}} is reproduced within the 0.01 A margin and the relativistic contraction of 0.077 A is also very well reproduced (0.075 A). Finally, the relative magnitude of the effects of the core orbital change, mass--velocity potential, and Darwin potential on the net relativistic effects are analyzed in the four molecules studied.

• OSTI ID: 6313334
• Journal Information: Journal of Chemical Physics; (USA), Journal Name: Journal of Chemical Physics; (USA) Vol. 93:8; ISSN JCPSA; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
CHALCOGENIDES
CORRECTIONS
ELECTRONIC STRUCTURE
ELEMENTS
FIELD THEORIES
GENERAL RELATIVITY THEORY
HYDRIDES
HYDROGEN COMPOUNDS
METALS
MOLECULAR ORBITAL METHOD
OXIDES
OXYGEN COMPOUNDS
POTENTIALS
RADIATIVE CORRECTIONS
REFRACTORY METAL COMPOUNDS
RELATIVITY THEORY
SILVER COMPOUNDS
SILVER HYDRIDES
SILVER OXIDES
TECHNETIUM COMPOUNDS
TECHNETIUM OXIDES
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS
VALENCE
YTTRIUM COMPOUNDS
YTTRIUM OXIDES