Electrostatic Free Energy and Other Properties of States Having Nonequilibrium Polarization. I

Abstract

Various processes such as electron transfer reactions, redox reactions at electrodes, and electronic excitation of dissolved ions may proceed by way of intermediate states whose electrical polarization is not in equilibrium with the field arising from the charges present. The usual expressions for the electrostatic free energy and for the differential equation satisfied by the potential assume that the polarization and the field are in equilibrium. Accordingly, these equations are of but limited applicability to these processes. In the present paper equations are derived for various properties of systems having such nonequilibrium electrostatic configurations. These properties include the free energy, energy, and entropy of the nonequilibrium system, and the spacial dependence of the electrostatic potential. The free energy, for example, will be used to calculate the probability of formation of nonequilibrium states in certain problems of physical interest.