Toward a unique definition of the local spin

Eloy Ramos-Cordoba, Eduard Matito, István Mayer, Pedro Salvador

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

In this work, we demonstrate that there is a continuum of different formulations for the decomposition of 〈Ŝ 2〉 that fulfills all physical requirements imposed to date. We introduce a new criterion based upon the behavior of single-electron systems to fix the value of the parameter defining that continuum, and thus we put forward a new general formula applicable for both single-determinant and correlated wave functions. The numerical implementation has been carried out in the three-dimensional physical space for several atomic definitions. A series of representative closed-shell and open-shell systems have been used to illustrate the performance of this new decomposition scheme against other existing approaches. Unlike other decompositions of 〈Ŝ 2〉, the new scheme provides very small local-spin values for genuine diamagnetic molecules treated with correlated wave functions, in conformity with the physical expectations.

Original languageEnglish
Pages (from-to)1270-1279
Number of pages10
JournalJournal of chemical theory and computation
Volume8
Issue number4
DOIs
Publication statusPublished - Apr 10 2012

    Fingerprint

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

Cite this