Bridging Like-Charged Macroions through Long Divalent Rodlike Ions

Abstract

Like-charged macroions in aqueous electrolyte solution can attract each other because of the presence of inter- and/or intramolecular correlations. Poisson-Boltzmann theory is able to predict attractive interactions if the spatially extended structure (which reflects the presence of intramolecular correlations) of the mobile ions in the electrolyte is accounted for. We demonstrate this for the case of divalent, mobile ions where each ion consists of two individual charges separated by a fixed distance. Variational theory applied to this symmetric 2:2 electrolyte of rodlike ions leads to an integro-differential equation, valid for arbitrary rod length. Numerical solutions reveal the existence of a critical rod length above which electrostatic attraction starts to emerge. This electrostatic attraction is distinct from nonelectrostatic depletion forces. Analysis of the orientational distribution functions suggests a bridging mechanism of the rodlike ions to hold the two macroions together. For sufficiently large rod length, we also observe "overcharging", that is, an over-compensation of the macroion charges by the diffuse layer of mobile rodlike ions. Our results emphasize the importance of the often rodlike internal structure that condensing agents such as polyamines, peptides, or polymer segments exhibit. The results were compared with Monte Carlo simulations.