Strong-coupling theory of counterions with hard cores between symmetrically charged walls

Abstract

By a combination of Monte Carlo simulations and analytical calculations, we investigate the effective interactions between highly charged planar interfaces, neutralized by mobile counterions (salt-free system). While most previous analysis have focused on point-like counterions, we treat them as charged hard spheres. We thus work out the fate of like-charge attraction when steric effects are at work. The analytical approach partitions counterions in two sub-populations, one for each plate, and integrates out one sub-population to derive an effective Hamiltonian for the remaining one. The effective Hamiltonian features plaquette four-particle interactions, and it is worked out by computing a Gibbs-Bogoliubov inequality for the free energy. At the root of the treatment is the fact that under strong electrostatic coupling, the system of charges forms an ordered arrangement, that can be affected by steric interactions. Fluctuations around the reference positions are accounted for. To dominant order at high coupling, it is found that steric effects do not significantly affect the interplate effective pressure, apart at small distances where hard sphere overlap are unavoidable, and thus rule out configurations.

18 pages, 15 figures

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Cited by in corpus (1)

• Toward Modeling the Structure of Electrolytes at Charged Mineral Interfaces using Classical Density Functional Theory