Local spins: improved Hilbert-space analysis.
The decomposition of <Ŝ(2)> for a general wave function has been carried out in the framework of the Hilbert-space analysis. The one and two-center components fulfill all physical requirements imposed to date. An inherent ambiguity of the Hilbert-space decomposition of a two-electron quantity, in particular using a Mulliken-type scheme, is also discussed in detail. The formalism of effective atomic densities has allowed us to derive in a simple manner appropriate expressions for the decomposition of <Ŝ(2)> in the framework of Hilbert space analysis that are consistent with Mulliken population analysis and related quantities. Using a particular mapping we have derived the Hilbert-space expressions also in the framework of Löwdin population analysis in a straightforward manner. The numerical results obtained with the latter formalism have proved to be more robust and reliable.
Department of Chemistry and Institute of Computational Chemistry, University of Girona, 17071 Girona, Spain.
Eloy
E
Ramos-Cordoba
Eduard
E
Matito
Pedro
P
Salvador
István
I
Mayer
D000498:Allyl Compounds / Q000737:chemistry*; D001555:Benzene Derivatives / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D011789:Quantum Theory
D000498:Allyl Compounds; D001555:Benzene Derivatives; D005609:Free Radicals; C524146:benzyne