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Journal Articles Theoretical Chemistry Accounts: Theory, Computation, and Modeling Year : 2015

Spin contamination and noncollinearity in general complex Hartree-Fock wave functions

Abstract

An expression for the square of the spin operator expectation value, < S^2>, is obtained for a general complex Hartree-Fock (GCHF) wave function and decomposed into four contributions: The main one whose expression is formally identical to the restricted (open-shell) Hartree-Fock expression. A spin contamination one formally analogous to that found for spin unrestricted Hartree-Fock wave functions. A noncollinearity contribution related to the fact that the wave function is not an eigenfunction of the spin-S_z operator. A perpendicularity contribution related to the fact that the spin density is not constrained to be zero in the xy-plane. All these contributions are evaluated and compared for the H_2O^+ system. The optimization of the collinearity axis is also considered.
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Dates and versions

hal-00790674 , version 1 (20-02-2013)
hal-00790674 , version 2 (13-03-2013)
hal-00790674 , version 3 (19-06-2015)
hal-00790674 , version 4 (09-08-2015)
hal-00790674 , version 5 (04-09-2015)

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Cite

Patrick Cassam-Chenaï. Spin contamination and noncollinearity in general complex Hartree-Fock wave functions. Theoretical Chemistry Accounts: Theory, Computation, and Modeling, 2015, 134 (11), pp.125. ⟨hal-00790674v5⟩
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