Local spins: improved Hilbert-space analysis

Phys Chem Chem Phys. 2012 Nov 28;14(44):15291-8. doi: 10.1039/c2cp42513k. Epub 2012 Oct 10.

Abstract

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Allyl Compounds / chemistry*
  • Benzene Derivatives / chemistry*
  • Free Radicals / chemistry
  • Quantum Theory*

Substances

  • Allyl Compounds
  • Benzene Derivatives
  • Free Radicals
  • benzyne