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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Theoretical Chemistry Accounts: Theory, Computation, and Modeling, Springer Verlag, 2015, 134 (11), pp.125. 〈http://link.springer.com/article/10.1007/s00214-015-1731-6〉
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Dernière modification le : vendredi 12 janvier 2018 - 01:51:48
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  • HAL Id : hal-00790674, version 5
  • ARXIV : 1508.02058

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Patrick Cassam-Chenaï. Spin contamination and noncollinearity in general complex Hartree-Fock wave functions. Theoretical Chemistry Accounts: Theory, Computation, and Modeling, Springer Verlag, 2015, 134 (11), pp.125. 〈http://link.springer.com/article/10.1007/s00214-015-1731-6〉. 〈hal-00790674v5〉

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