Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

7-1998

Journal or Book Title

Journal of Chemical Physics

Volume

109

Issue

3

First Page

919

Last Page

927

DOI

10.1063/1.476633

Abstract

Excited states of singlet and triplet H2Ti(μ−H)2TiH2 have been calculated using multiconfigurational wave functions. The effects of orbital relaxation are determined by optimizing orbitals for all states separately and comparing to state-averaged calculations, and are found to be small. Dynamic electron correlation included through second-order perturbation theory is found to have a considerable effect on excited state relative energies, but not on the ordering of states. Spin-orbit coupling effects are introduced by a one-electron operator which uses an effective nuclear charge to replace two-electron effects. The resulting splittings of the lowest energy triplet state components are 0.027 and 0.199 cm−1, respectively. The former is due to the angular momentum operator which acts along the Ti–Ti axis; the latter is due almost entirely to the angular momentum operator which acts in the direction perpendicular to the plane of the Ti–H–Ti bridge. An overall ferromagnetic effect of 0.660 cm−1 on the ground statesinglet-first excited triplet energy gap is predicted. Orbital interactions responsible for spin-orbit coupling effects are identified.

Comments

The following article appeared in Journal of Chemical Physics 109 (1998): 919, and may be found at doi:10.1063/1.476633.

Rights

Copyright 1998 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics.

Copyright Owner

American Institute of Physics

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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