Adiabaticity criteria for outer-sphere bimolecular electron-transfer reactions

A model is presented for outer-sphere bimolecular electron-transfer reactions which is correct in the adiabatic, nonadiabatic, and intermediate dynamical regimes for an overdamped solvent coordinate. From this model we deduce the conditions for the transfer to be "adiabatic" or "nonadiabatic". Evidence for the two regimes exists in the experimental literature, so this work will provide guidance for mapping out the transition between these regimes. The time-scale separations needed to adequately describe the process as an average over (distant dependent) unimolecular rates are described. © 1988 American Chemical Society.

Duke Scholars

Author David N. Beratan Chemistry