VIBRONIC COUPLING IN ELECTRONIC-TRANSITIONS WITH SIGNIFICANT DUSCHINSKY-EFFECT

Conceptual and mathematical difficulties arise in the study of transit ions between vibronic states belonging to crossing Born-Oppenheimer hy persurfaces with significantly different positions and shapes of the m inimum-energy nuclear configurations (Duschinsky effect). This article presents an analytic procedure for the evaluation of the pertinent co upling integrals, adopting a normal coordinate reference system for th e internal nuclear motion and harmonic approximation. The Duschinsky e ffect is properly considered. The procedure was applied to the dynamic s of electron transfer in neutral mixed valence monoradicals, using th e diabatic representation. (C) 1997 John Wiley & Sons, Inc.