Contrasting Dielectric Properties of Electrolyte Solutions with Polar and Polarizable Solvents.

Abstract

We examine the static dielectric constant of electrolyte solutions with a polar and/or polarizable small-molecule solvent using a classical field-theoretic approach. We compute corrections to the dielectric constant and screening length due to intra- and intermolecular correlations via a renormalized one-loop approximation, accounting for the excluded volume of both solvent and electrolyte. In the salt-free case, we verify the one-loop theory by comparison with full numerical solutions of the field theory. The one-loop theory predicts either a nonlinear dielectric decrement or increment with increasing salt, depending on whether the fluid correlations are dominated by the dipolar or polarizable nature of the solvent. These contrasting regimes of nonlinear dielectric behavior are consistent with experimental trends in high- and low-dielectric constant electrolyte solutions.