Charge Renormalization and Charge Oscillation in Asymmetric Primitive Model

TL;DR

This paper extends the Debye charging method to analyze the linear response of asymmetric electrolytes, revealing charge renormalization, oscillations at high densities, and agreement with Monte Carlo simulations.

Contribution

It introduces a generalized analytic approach to study charge renormalization and oscillations in asymmetric primitive models of electrolytes.

Findings

Ionic correlations significantly renormalize screening length and dielectric constant.

Larger ion valence is substantially increased by ionic correlations.

Charge oscillations occur at lower densities compared to symmetric electrolytes.

Abstract

The Debye charging method is generalized to study the linear response properties of the asymmetric primitive model for electrolytes. Analytic results are obtained for the effective charge distributions of constituent ions inside the electrolyte, from which all static linear response properties of system follow. It is found that, as the ion density increases, both the screening length and the dielectric constant receive substantial renormalization due to ionic correlations. Furthermore, the valence of larger ion is substantially renormalized upwards by ionic correlations, whilst that of smaller ions remains approximately the same. For sufficiently high density, the system exhibit charge oscillations. The threshold ion density for charge oscillation is much lower than the corresponding value for symmetric electrolytes. Our results agree well with large scale Monte Carlo simulations.