Nonmonotonic Pair Potentials in the Interaction of Like-Charged Objects in Solution.

Abstract

We consider the long-standing like-charge attraction problem, wherein under certain conditions, similarly charged spheres suspended in aqueous electrolyte have been observed to display a minimum in their interaction potential, contrary to the intuitively expected monotonically varying repulsion. Recently, we described an interfacial mechanism invoking the molecular nature of the solvent that explains this anomalous experimental observation. In our model for the interaction of negatively charged particles in water, the minimum in the pair potential results from the superposition of competing contributions to the total free energy. One of these contributions is the canonical repulsive electrostatic term, whereas the other is a solvation-induced attractive contribution. We find that whereas both contributions grow approximately exponentially with decreasing interparticle separation, the occurrence of a stable, long-ranged minimum in the pair potential arises from differences in the precise interparticle separation dependence of the two terms. Specifically, the interfacial solvation term exhibits a more gradual decay with distance than the electrostatic repulsion, permitting the attractive contribution to dominate the interaction at large distances. Importantly, these disparities become evident in quantities calculated from exact numerical solutions to the governing nonlinear Poisson-Boltzmann (PB) equation for the spatial electrical potential distribution in the system. In marked contrast, we find that the linearized PB equation, applicable in the regime of low surface electrical potentials, does not support nonmonotonic trends in the total interaction free energy within the present model. Our results point to the importance of exact descriptions of electrostatic interactions in real systems that most often do not subscribe to particular mathematical limits where analytical approximations may provide a sufficiently accurate description of the problem.