A complete active space valence bond method with nonorthogonal orbitale

Kimihiko Hirao, Haruyuki Nakano, Kenichi Nakayama

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

A complete active space self-consistent field (SCF) wave function is transformed into a valence bond type representation built from nonorthogonal orbitals, each strongly localized on a single atom. Nonorthogonal complete active space SCF orbitals are constructed by Ruedenberg's projected localization procedure so that they have maximal overlaps with the corresponding minimum basis set of atomic orbitals of the free-atoms. The valence bond structures which are composed of such nonorthogonal quasiatomic orbitals constitute the wave function closest to the concept of the oldest and most simple valence bond method. The method is applied to benzene, butadiene, hydrogen, and methane molecules and compared to the previously proposed complete active space valence bond approach with orthogonal orbitals. The results demonstrate the validity of the method as a powerful tool for describing the electronic structure of various molecules.

Original languageEnglish
Pages (from-to)9966-9974
Number of pages9
JournalJournal of Chemical Physics
Volume107
Issue number23
DOIs
Publication statusPublished - Dec 15 1997
Externally publishedYes

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Wave functions
valence
orbitals
Atoms
Molecules
Methane
Benzene
Electronic structure
Hydrogen
self consistent fields
wave functions
butadiene
atoms
molecules
methane
benzene
electronic structure
hydrogen
1,3-butadiene

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

A complete active space valence bond method with nonorthogonal orbitale. / Hirao, Kimihiko; Nakano, Haruyuki; Nakayama, Kenichi.

In: Journal of Chemical Physics, Vol. 107, No. 23, 15.12.1997, p. 9966-9974.

Research output: Contribution to journalArticle

Hirao, Kimihiko ; Nakano, Haruyuki ; Nakayama, Kenichi. / A complete active space valence bond method with nonorthogonal orbitale. In: Journal of Chemical Physics. 1997 ; Vol. 107, No. 23. pp. 9966-9974.
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