Electrical double layers. V. Asymmetric ion–wall interactions

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Abstract
Monte Carlo computations are used to study a primitive-model electrolyte with unequal distances of closest approach of its ions to a charged surface. This asymmetry, like that which must occur in real electrolytes, induces an asymmetric charge-potential relationship, and a concentration-dependent potential of zero charge, due entirely to the diffuse layer. The results provide a test of the Gouy–Chapman-level theory [J. Chem. Phys. 76, 4623 (1982)] for this model, and also display how polarization of a metallic surface will substantially enhance the effects.