Reorganization inertial

From a comparison of Eqs. (9) and (22) we see that H = F(0 ). To elucidate the physical meaning of the exponent in Eq. (22), we consider first the case when 0 = 1 (barrierless reaction). In this case Eq. (20) determines the change of the free energy of the system F(l) when it is polarized by the electric field AEU = E -E (only the free energy related to the inertial polarization is considered). It may be easily seen that the absolute value of F(l) is equal to the energy of the reorganization of the medium Es (>0). 

The activation free energy AG is dehned by two terms. One term is the reaction free energy [AG ], which is derived from the redox potential difference of the donor and acceptor. The second term is the medium reorganization energy (k), which is the energy stored in the solvent inertial degrees of freedom when the electron is shifted suddenly from donor to acceptor (1-5). Marcus theory predicts the activation free energy ... 

The inertial reorganization energy matrix elements t j are defined as... 

For the sake of simplicity we shall confine ourselves to transfer processes for tightly bound electrons and neglect the effects of distortion of electronic wave functions by polarization fluctuations. Furthermore, we shall suppose that the whole inertial polarization can be described in a classical manner (i.e. hcoj, kT). In the case of water the quantum tail of polarization fluctuations is small and, as shown in Ref. [11], can be formally taken into account by introducing a factor (< 1) into the reorganization energy (see below). For the other liquids, used in the experiments with immiscible liquids, the detailed measurements of e(m) are not available as a rule. 

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