Quantum theory for free energies of electron transfer

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Abstract
We consider the problem of electron transfer between two symmetric redox states for cases in which the interstate coupling can be strong and the coupled harmonic bath can be nonadiabatic. We utilize an adiabatic bath coupled to the charge transfer species as a reference system and treat the solvation effects of nonzero frequency Fourier modes approximately, yielding an analytical theory for the activation free energy in terms of the spectral density of the bath. The theory is exact for both slow and fast bath modes. For small interstate coupling, the theory agrees with the golden rule result. We test the theory's accuracy at large couplings in the intermediate frequency regime by comparison with Monte Carlo simulation.

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