A Study of the Relative Importance of One and Two-Electron Contributions to Spin–Orbit Coupling

Date
2000-04-01
Authors
Fedorov, Dmitri
Gordon, Mark
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Ames Laboratory
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Chemistry
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Abstract

The existing methods to estimate the magnitude of spin–orbit coupling for arbitrary molecules and multiconfigurational wave functions are reviewed. The form-factor method is extended from the original singlet–triplet formulation into arbitrary multiplicities. A simplified version of the mean-field method (the partial two-electron method, P2E) is formulated and tested versus the full two-electron operator on a set of representative molecules. The change of the one and two-electron spin–orbit coupling down the Periodic Table is investigated, and it is shown that the computationally much less demanding P2E method has an accuracy comparable to that of the full two-electron method.

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The following article appeared in Journal of Chemical Physics 112 (2000): 5611, and may be found at doi:10.1063/1.481136.

Keywords
Mean field theory, Wave functions
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