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The term superexchange usually refers to bridge-mediated ET in which the intermediate states provide an effective increase in the donor-acceptor nonadiabatic electronic coupling (or termed transfer integral) rather than actual populated sites for stepwise electron hopping. Within this picture, the unoccupied bridge states are higher in energy than that of the donor/acceptor for electron transfer or the occupied bridge states are lower in energy than that of the donor/accepter for hole transfer. The characteristic of superexchange ET through semiconductors/insulators is the drastic decay of ET rates over the distance that the electron travels, i.e, the effective electronic coupling or conductance decays exponentially versus the ET distance. It should also be mentioned that in the superexchange mechanism the donor-acceptor coupling is usually a combination of through-bond (nearest-neighbor tunneling) and through-space (long distance) interactions. For more detailed discussion, see: Ratn
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The term superexchange usually refers to bridge-mediated ET in which the intermediate states provide an effective increase in the donor-acceptor nonadiabatic electronic coupling (or termed transfer integral) rather than actual populated sites for stepwise electron hopping. Within this picture, the unoccupied bridge states are higher in energy than that of the donor/acceptor for electron transfer or the occupied bridge states are lower in energy than that of the donor/accepter for hole transfer. The characteristic of superexchange ET through semiconductors/insulators is the drastic decay of ET rates over the distance that the electron travels, i.e., the effective electronic coupling or conductance decays exponentially versus the ET distance. It should also be mentioned that in the superexchange mechanism the donor-acceptor coupling is usually a combination of through-bond (nearest-neighbor tunneling) and through-space (long distance) interactions. For more detailed discussion, see: Ratner, M. A. J. Phys. Chem. 1990, 94, 4877-4883.
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