A new complex centroid reaction coordinate method is used to study electron transfer systems with strong electronic coupling. Formal analogy between current problem and the Ising model of one-dimensional spin system is used to develop a useful approximation for the partition function of electron transfer system in all orders of perturbation theory and when quantum effects are present. The reactions in the inverted region are discussed. The range of applicability of the usual nonadiabatic theory is re-examined. It is concluded that quantum solvent modes can effectively reduce electronic coupling in such a way that a nonadiabatic behavior can sometimes be induced in conventionally strongly coupled systems. Such an induced quantum nonadiabaticity is demonstrated in a numerical calculation.
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Stuchebrukhov et al. (1994) studied this question.
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