Non-Gaussian statistics of binding/unbinding events and the energetics of electron transfer reactions

We describe a model of electron transfer reactions affected by local binding to the donor or acceptor sites of a particle in equilibrium with the solution. The statistics of fluctuations of the donor-acceptor energy gap caused by binding/unbinding events are non-Gaussian, and the resulting free energy surfaces of electron transfer are non-parabolic. The band-width of the charge-transfer optical transition is predicted to pass through a maximum as a function of the concentration of binding particles in the solution. The breakdown of the link between the Stokes shift and the reorganization energy of electron transfer is also predicted by the model. (c) 2008 Elsevier B.V. All rights reserved.