Theory of non-thermal electron transfer Original Research Article

A class of ultrafast electron transfer reactions in which the system approaches the term crossing point moving over upper branch of the potential energy surface is considered. The joint dynamics of electron transition and nuclear degrees of freedom reorganization is explored. The probability of electron transfer has been calculated in the framework of both the perturbation theory in electronic coupling and the stochastic approach. It has been shown that while the driving force is increasing from −Er to +Er the electron transfer time scale varies from the fastest time scale of nuclear degrees of freedom coupled to the electron transfer to the slowest one. One of the possible manifestations of the coherent intramolecular vibrational effects is considered in the nonadiabatic limit. The theory allows to include in the consideration an arbitrary number of nuclear degrees of freedom.