Complete active space valence bond method applied to chemical reactions

Haruyuki Nakano, Kenichi Nakayama, Kimihiko Hirao

Research output: Contribution to journalArticlepeer-review

6 Citations (Scopus)

Abstract

A complete active space valence bond (CASVB) method with orthogonal and non-orthogonal orbitals is applied to the collinear exchange reaction H + H2 → H2 + H and the unimolecular dissociation H2CO → H2 + CO. The bond nature during the reactions is analyzed using the occupation number (weight) of the valence bond resonance structures. The CASVB descriptions with orthogonal and non-orthogonal orbitals give a similar picture, although the ratio of covalent vs. ionic bonds are quite different. In the H2CO → H2 + CO reaction, the CH bond dissociation and HH bond formation occur after passing through the transition state. CASVB gives a clear understanding of reaction mechanisms in terms of competing bonding schemes whose weights change along the intrinsic reaction coordinate.

Original languageEnglish
Pages (from-to)55-69
Number of pages15
JournalJournal of Molecular Structure: THEOCHEM
Volume461-462
DOIs
Publication statusPublished - Apr 2 1999
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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