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 polelectrolyte 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 point-like, 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 consider the possibility that increasing the number of nearest neighbors for each rod in the bundle frustrates the attractive interaction between the rods. Such a frustration leads to the formation of finite size bundles as well, even when the counterions are small.