THEORETICAL-STUDY OF SOLVENT EFFECTS ON THE ELECTRONIC COUPLING MATRIX ELEMENT IN RIGIDLY LINKED DONOR-ACCEPTOR SYSTEMS

The recently developed generalized Mulliken-Hush approach for the calc ulation of the electronic coupling matrix element for electron-transfe r processes is applied to two rigidly linked donor-bridge-acceptor sys tems having dimethoxyanthracene as the donor and a dicarbomethoxycyclo butene unit as the acceptor. The dependence of the electronic coupling matrix element as a function of bridge type is examined with and with out solvent molecules present. For clamp-shaped bridge structures solv ent can have a dramatic effect on the electronic coupling matrix eleme nt. The behavior with variation of solvent is in good agreement with t hat observed experimentally for these systems.