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

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. TheM 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. 2006 Elsevier B.V. All rights reserved.