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tme cce e 6 We report microscopic calculations of free energies and entropies for intramolecular electron transfer reactions. The calculation algo-Beginning with work of Marcus on electron transfer where this process is a key component of energy transport chains [4–7]. Biological systems pose a major challenge to bound water [8], membranes, and parts of the polar and the vicinity of a redox site can in principle be included by assigning different dielectric constants to its heterogeneous parts [10]. Two fundamental problems inevitably arise in this algorithm. The first has been well recognized over the years of its application and is related to the ambiguity of defining the dielectric cavity for molecular solutes. Thi