Conformational dynamics modulating electron transfer

Abstract: Diffusional dynamics of the donor-acceptor distance in electron-transfer reactions are responsible for the appearance of a new time scale of diffusion over the distance of falloff of electronic tunneling. The distance dynamics compete with the medium polarization dynamics in the solvent-controlled electron transfer kinetics. A new solution incorporating the medium and donor-acceptor dynamics into the electron-transfer rate constant is proposed. The pre-exponential factor of the rate constant switches between a distance-independent solvent-controlled regime and exponential distance decay. The crossover between two regimes is controlled by an effective relaxation time slowed down by a factor exponentially depending on the variance of the donor-acceptor displacement. Flexible donor-acceptor complexes must show a greater tendency for solvent-controlled electron transfer. Electron-transfer energy chains are best designed by placing the redox cofactors near the crossover distance.