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

Yng-Gwei Chen^†,^‡,^§ and
John D. Weeks^‡,^¶,^‖

Departments of ^†Physics and
^¶Chemistry and Biochemistry and
^‡Institute for Physical Science and Technology, University of Maryland, College Park, MD 20742

Edited by Benjamin Widom, Cornell University, Ithaca, NY, and approved March 27, 2006 (received for review January 11, 2006)

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. However, 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. Analytical results for the minimal coupling strength needed to get any attraction and for the separation at which the attractive force is a maximum are presented.

Footnotes

^‖To whom correspondence should be addressed at:
Institute for Physical Science and Technology, University of Maryland, College Park, MD 20742.
E-mail: jdw{at}ipst.umd.edu
↵ ^§Present address: Laboratory of Chemical Physics, National Institute of Diabetes and Digestive and Kidney Diseases, Building 5, National Institutes of Health, Bethesda, MD 20892.
Author contributions: Y.-G.C. and J.D.W. designed research, performed research, and wrote the paper.
Conflict of interest statement: No conflicts declared.
This paper was submitted directly (Track II) to the PNAS office.
Abbreviations:

Abbreviations:

LMF,

local molecular field;

PB,

Poisson–Boltzmann;

SAPM,

size-asymmetric primitive model;

WL,

Weis and Levesque;

MC,

Monte Carlo;

SCA,

strong coupling approximation;

mPB,

mimic PB.