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

Patrick Cassam-Chenaï (1)

1 JAD - Laboratoire Jean Alexandre Dieudonné

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.

Mots clés: spin contamination; general complex Hartree-Fock; collinearity

Domaines: Chimie théorique et/ou physique; Physique Quantique [quant-ph]

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⟩