Free Energy of Nonequilibrium Polarization Systems. III. Statistical Mechanics of Homogeneous and Electrode Systems

A statistical mechanical treatment is given for homogeneous and electrochemical systems having nonequilibrium dielectric polarization. A relation between the free energy of these systems and those of related equilibrium ones is deduced, having first been derived in Part II by a dielectric continuum treatment. The results can be applied to calculating polar contributions in the theory of electron transfers and in that of shifts of electronic spectra in condensed media. The effect of differences in polarizability (of a light emitting or absorbing molecule in its initial and final electronic states) on the polar term in the shift is included by a detailed statistical analysis, thereby extending Part II. Throughout, the ``particle'' description of the entities contributing to these phenomena is employed, so as to derive the results for rather general potential energy functions.