The role of d π orbitals in spin-orbit coupling

Authors: Wadt, W.R.¹; Moomaw, W.R.²

Source: Molecular Physics, Volume 25, Number 6, June 1973 , pp. 1291-1303(13)

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Abstract:

A general framework is developed for the theoretical treatment of d -orbital contributions of heavy atoms to the spin-orbit coupling of planar molecules. Unlike p π orbitals for which only three-centre spin-orbit terms are non-vanishing, it is shown that a number of one- and two-centre terms will contribute. The case of thiophene (C 4 H 4 S) is examined, and all one- and two-centre integrals are evaluated explicitly. Although the two-centre terms are individually only a few per cent of the one-centre term, it is found that because of the large number of two-centre terms, they usually dominate the one-centre term. In thiophene, it is found that the contribution of individual d π terms is on the order of 0·02-2·0 cm -1 , which is comparable in magnitude to other contributions. An examination of the results as a function of effective nuclear charge and internuclear distance is also made.

Document Type: Research article

DOI: http://dx.doi.org/10.1080/00268977300101131

Affiliations: 1: Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena, California, 91109, U.S.A. 2: Department of Chemistry, Williams College, Williamstown, Massachusetts, 01267, U.S.A.

Publication date: 1973-06-01

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