Ab initio MO calculations of electronic coupling matrix elements on model systems for intramolecular electron transfer, hole transfer, and triplet energy transfer: distance dependence and pathway in electron transfer and relationship of triplet energy transfer with electron and hole transfer

Abstract

The matrix elements for electron transfer (ET) for anions of 1,3- and 1,4-dimethylenecyclohexane and 2,1- and 2,6-dimethylenedecalin; those for anions of methylene chains, H 2 C-(CH 2 ) n -CH 2 (n = 3-5); and those for ET, hole transfer (HT), and triplet energy transfer (TT) of anion, cation, and neutral systems of 1,4-divinylcyclohexane have been calculated with the ab initio MO method by using the UHF wave functions as diabatic states. Calculations for methylene chains indicate that the observed «distance dependence» is determined not only by the number of CC bonds but also by subtle angular dependency of MO overlap