Abstract

The probability of the nonthermal transfer of an electron of an excited donor-acceptor complexes was calculated from the electron coupling parameter within the framework of time-dependent perturbation theory. Using the analysis of the two first corrections of the perturbation theory series for the standard spinboson model with the Debye spectral density of thermostat oscillators as a basis, we revealed the structure of higher corrections. This allowed us to sum up the series and obtain a new analytical expression distinct from the widely used Pade-approximation for the probability of the nonthermal transfer of an electron. The stochastic approach was shown to allow overestimation of the probability of nonthermal electron transitions by 40.0% in the solvent-controlled regime.

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