Spin contamination and noncollinearity in general complex Hartree-Fock wave functions - Université Côte d'Azur Accéder directement au contenu
Article Dans Une Revue Theoretical Chemistry Accounts: Theory, Computation, and Modeling Année : 2015

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

Résumé

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.
Fichier principal
Vignette du fichier
gchf4.pdf (136.17 Ko) Télécharger le fichier
Origine Fichiers produits par l'(les) auteur(s)
Loading...

Dates et 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)

Identifiants

Citer

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⟩
286 Consultations
541 Téléchargements

Altmetric

Partager

Gmail Mastodon Facebook X LinkedIn More