Nonadiabatic chemical reactions in a strong time-dependent electric field: An electron transfer reaction in a polar solvent

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Abstract
Nonadiabatic chemical reactions of a charge transfer in a polar solvent are considered in the presence of a strong time-dependent electric field. The integro-differential kinetic equation for a transfer probability is obtained in the noninteracting blip approximation for an arbitrary electric field. A kernel of the integral part is expressed through a dielectric loss function of the solvent. In a long time limit a high-temperature solution is obtained. It is found the the rate constant decreases, increases, or oscillates with respect to the intensity and frequency of the field. When the energy of the photon is comparable to the reorganization energy of the solvent, localization of the charge occurs. The localization field parameters are dependent on the heat of the reaction. A strong enhancement of the rate constant is found for barrierless reactions (as much as 18 orders of magnitude) with respect to the intensity of the field. The estimations show that a probable candidate for an observation of these effects is a long-range electron transfer reaction.