Local molecular field theory for effective attractions between like charged objects in systems with strong Coulomb interactions

TL;DR

This paper introduces a local molecular field theory that simplifies the analysis of Coulomb interactions in charged systems by mapping them onto a short-ranged interaction model, accurately capturing ion pairing and effective attractions.

Contribution

The paper develops a novel local molecular field approach that effectively models Coulomb interactions as short-ranged, enabling detailed analysis of ion pairing and attractions in charged systems.

Findings

Pair correlation functions resemble those in primitive models.

Ion pairs and clusters form at low densities.

Effective attraction between charged walls is accurately described.

Abstract

Strong short ranged positional correlations involving counterions can induce a net attractive force between negatively charged strands of DNA, and lead to the formation of ion pairs in dilute ionic solutions. But the long range of the Coulomb interactions impedes the development of a simple local picture. We address this general problem by mapping the properties of a nonuniform system with Coulomb interactions onto those of a simpler system with short ranged intermolecular interactions in an effective external field that accounts for the averaged effects of appropriately chosen long ranged and slowly varying components of the Coulomb interactions. The remaining short ranged components combine with the other molecular core interactions and strongly affect pair correlations in dense or strongly coupled systems. We show that pair correlation functions in the effective short ranged system closely resemble those in the uniform primitive model of ionic solutions, and illustrate the formation of ion pairs and clusters at low densities. The theory accurately describes detailed features of the effective attraction between two equally charged walls at strong coupling and intermediate separations of the walls. New analytical results for the minimal coupling strength needed to get any attraction and for the separation where the attractive force is a maximum are presented.