From Over-charging to Like-charge Attraction in the Weak Coupling Regime

TL;DR

This paper demonstrates that strongly charged surfaces with condensed counter-ions can behave like conductors, leading to attractive interactions at short distances due to image charge effects, with analytical calculations supporting this behavior.

Contribution

It introduces a model where condensed counter-ions induce conductor-like behavior, explaining like-charge attraction through analytical extension of Debye-Huckel theory and image charge methods.

Findings

Effective attraction at small separations between charged surfaces.

Repulsion at large separations.

Analytical expressions for correlation energies.

Abstract

Despite decades of intensive studies, the effective interactions between strongly charged colloids still remain elusive. Here we show that a strongly charged surface with a layer of condensed counter- ions behaves effectively as a conductor, due to the mobile nature of the condensed ions. An external source charge in its vicinity is therefore attracted towards the surface, due to the image charge effect. This mechanism leads to correlational energies for counter-ions condensed on two distinct surfaces, as well as for free ions in the bulk. Generalizing Debye-Huckel theory and image charge methods, we analytically calculate these correlation energies for the two-plates problem, at the iso-electric point, where condensed counterions precisely balance the bare surface charges. At this point, the effective interaction between two plates is always attractive at small separation and repulsive at large separation.