Use of the neighboring orbital model for analysis of electronic coupling in Class III intervalence compounds

Stephen F. Nelsen, Michael N. Weaver, Yun Luo, Jenny V. Lockard, Jeffrey I. Zink

Research output: Contribution to journalArticlepeer-review

29 Scopus citations

Abstract

Symmetrical charge-delocalized intervalence radical ions should not be described by the traditional two-state model that has been so successful for their localized counterparts. If they lack direct overlap between their charge-bearing units (M), their diabatic orbitals have an equal energy pair of symmetrized M-centered combination orbitals that are symmetric (S) or antisymmetric (A) with respect to a symmetry element at the center of the molecule. The M combination orbitals will mix separately with bridge orbitals of the same symmetry. We call the simplest useful model for this situation the neighboring orbital model, which uses the S and A bridge orbitals of high overlap that lie closest in energy to the M orbital pair, resulting in two two-state models that have a common energy for one pair. This model is developed quantitatively, and examples having 1, 3, 5, and 7 electrons in the neighboring orbitals are illustrated.

Original languageEnglish (US)
Pages (from-to)195-201
Number of pages7
JournalChemical Physics
Volume324
Issue number1 SPEC. ISS.
DOIs
StatePublished - May 9 2006
Externally publishedYes

All Science Journal Classification (ASJC) codes

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

Keywords

  • Electronic coupling
  • Intervalence compounds
  • Koopmans' theorem
  • Marcus-Hush
  • Neighboring orbital model
  • Radical ions

Fingerprint Dive into the research topics of 'Use of the neighboring orbital model for analysis of electronic coupling in Class III intervalence compounds'. Together they form a unique fingerprint.

Cite this