Theory of time-dependent polarization about an ion in an isotropic liquid

Publisher Website
Google Scholar
Abstract
We have investigated the theory of polarization of a dipolar solvent by a newly created ion or free electron. As a reference system we have used the solvent together with the ‘‘uncharged ion,’’ and by means of statistical mechanics, we have examined the linear response of the system to the imposition of the ionic charge. The response depends upon the response at all k values, the low k behavior corresponding to continuum (universal) macroscopic dielectric effects, and the high k behavior corresponding to molecular (specific) phenomena which may have to be treated by quantum mechanics. We have focused on the quasicontinuum limits for which the low k behavior is assumed, but the sizes of ions and dipoles, and the velocities of ions are incorporated. We also look at some general properties of high k behavior; for example, because the polarization energy for small ions is independent of ion size, it is usually thought that solventbergs form about the ions, but, at least in part, this phenomenon can be explained by geometric considerations.