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CHAPTER 5

Statistical Mechanical Theory of Electron Transfer, Equivalent Equilibrium Distribution, Reaction Coordinate for ET, Inverted Free Energy Effect, Interactions in Polar Media

In this chapter, I have summarized the theory on potential energy expressions, on interparticle interaction energy, and on interactions in polar media which can be found in Refs. [1–5].

In the pivotal paper written for the Discussions of the Faraday Society of 1960 M. introduced for the first time a treatment of his theory in terms of potential energy surfaces and of statistical mechanics. This generalization of the earlier macroscopic treatment in terms of nonequilibrium solvent polarization was needed in order to treat in a consistent manner the contributions of both the inner coordinates of the molecules (in particular of the coordination shells, when present) and the outer solvent coordinates in the electron transfer process. The new concept of equivalent equilibrium distribution (e.e.d.), already briefly mentioned and used in Ref. [5a] (see Chapter 4