Free energy of nonequilibrium polarization systems. II. Homogeneous and electrode systems

Abstract

The polar contribution to the free energy is calculated for a system containing "particles" imbedded in a continuum having nonequilibrium dielectric polarization. Each particle may either be a single molecule or a whole collection of molecules (such as an electrode) at specified nuclear configuration and may possess a general permanent and induced charge distribution. Thereby, the results of Part I of this series are extended to a variety of systems. It is also shown that the polar contribution to the free energy can be written as the sum of free energies of equilibrium polarization systems, thereby permitting the immediate application of literature expressions for the latter to calculating the former. This expression is also derived for systems possessing partial dielectric unsaturation under a certain typical condition. Applications are made to the theory of electron-transfer reactions in solution and at electrodes and to the theory of the shift of electronic spectra of polar solutes by polar solvents.