Equilibrium bundle size of rodlike polyelectrolytes with counterion-induced attractive interactions

Abstract

Multivalent counterions can induce an effective attraction between like-charged rodlike polyelectrolytes, leading to the formation of polyelectrolyte bundles. In this paper, we calculate the equilibrium bundle size using a simple model in which the attraction between polyelectrolytes (assumed to be pairwise additive) is treated phenomenologically. If the counterions are pointlike, they almost completely neutralize the charge of the bundle, and the equilibrium bundle size diverges. When the counterions are large, however, steric and short-range electrostatic interactions prevent charge neutralization of the bundle, thus forcing the equilibrium bundle size to be finite. We also show that if the attractive interactions between the rods become frustrated as the bundle grows, finite-size bundles can be obtained with pointlike counterions.