Electron transfer in the nonadiabatic regime: Crossover from quantum-mechanical to classical behaviour

We study nonadiabatic electron transfer within the biased spin-boson model. We calculate the incoherent transfer rate in analytic form at all temperatures for a power law form of the spectral density of the solvent coupling. In the Ohmic case, we present the exact low temperature corrections to the zero temperature rate for arbitrarily large bias energies between the two redox sites. Both for Ohmic and non-Ohmic coupling, we give the rate in the entire regime extending from zero temperature, where the rate depends significantly on the detailed spectral behaviour, via the crossover region, up to the classical regime. For low temperatures, the rate shows characteristic quantum features, in particular the shift of the rate maximum to a bias value below the reorganization energy, and the asymmetry of the rate around the maximum. We study in detail the gradual extinction of the quantum features as temperature is increased. (C) 1999 Elsevier Science B.V. All rights reserved.