Electronic coupling in electron transfer and the influence of nuclear modes: theoretical and computational probes

Abstract.

Long-range electronic coupling of local donor and acceptor sites is formulated in the context of thermal and optical electron transfer and then illustrated with examples based on electronic structure calculations. The relationship of the calculated results to available experimental kinetic and optical data is discussed in detail. The influence of nuclear modes on the magnitude of the coupling (i.e., departures from the Condon approximation) is investigated in terms of both discrete molecular modes and solvent modes, and a general expression is presented for the modulation of the superexchange tunneling gap by motion along the electron transfer reaction coordinate.