Dissociation Potential Curves of Low-Lying States in Transition Metal Hydrides. 2. Hydrides of Groups 3 and 5

Supplemental Files
Date
2004-05-01
Authors
Koseki, Shiro
Ishihara, Yohei
Fedorov, Dmitri
Umeda, Hiroaki
Schmidt, Michael
Gordon, Mark
Journal Title
Journal ISSN
Volume Title
Publisher
Altmetrics
Authors
Research Projects
Organizational Units
Chemistry
Organizational Unit
Journal Issue
Series
Abstract

The dissociation energy curves of low-lying spin-mixed states for Group 5 hydrides (VH, NbH, and TaH), as well as Group 3 hydrides (ScH, YH, and LaH), have been calculated by using both effective core potential (ECP) and all-electron (AE) approaches. The two approaches are based on the multiconfiguration self-consistent field (MCSCF) method, followed by second-order configuration interaction (SOCI) calculations:  the first method employs an ECP basis set proposed by Stevens and co-workers (SBKJC) augmented by a set of polarization functions, and spin−orbit coupling effects are estimated with a one-electron approximation, using effective nuclear charges. The second method employs a double-ζ basis set developed by Huzinaga (MIDI) and three sets of p functions are added to both transition element and hydrogen and one set of f functions is also added to the transition element. The relativistic elimination of small components (RESC) scheme and full Breit−Pauli Hamiltonian are employed in the AE approaches to incorporate relativistic effects. The present paper reports a comprehensive set of theoretical results including the dissociation energies, equilibrium distances, electronic transition energies, harmonic frequencies, anharmonicities, and rotational constants for several low-lying spin-mixed states in the hydrides, filling a considerable gap in available data for these molecules. Transition moments are also computed among the spin-mixed states, and qualitative agreement is obtained for Group 3 hydrides in comparison with the experimental results reported by Ram and Bernath. Peak positions of emission spectra in Group 5 hydrides are also predicted.

Description

Reprinted (adapted) with permission from Journal of Physical Chemistry A 108 (2004): 4707, doi:10.1021/jp049839h. Copyright 2004 American Chemical Society.

Keywords
Citation
DOI
Collections