The dielectric constant of polarizable fluids from the renormalized perturbation theory

Abstract

A perturbation theoretical equation for the dielectric constant of polarizable dipolar fluids is proposed. For the fluctuation of the dipole moment, namely for the Kirkwood g-factor, a formula is given on the basis of Wertheim's renormalized perturbation theory. Using this formula, a series expansion for ε(p) is suggested on the basis of the Kirkwood equation, which gives an implicit function for ε as a function of ¶. The same series expansion can be derived from the Clausius-Mosotti equation—thus it proves to be independent of the boundary conditions. The resulting equation gives excellent results for the dielectric constant of the polarizable Stockmayer fluid producing good agreement with computer simulation data. The series expansion gives better results than the Kirkwood equation itself.