One-dimensional Coulomb system in a sticky wall confinement: Exact results.

Abstract

This work investigates a one-component one-dimensional Coulomb system in sticky wall confinement. Sticky wall is introduced as an alternative and intuitive depiction of charge regulation, the notion that a surface charge is not a fixed but a fluctuating quantity in dynamic equilibrium with its immediate environment. Emphasis is placed on intuitive derivation and expressions are obtained by observing that the partition function of a charge regulated system can be decomposed into a collection of independent equilibriums with different fixed surface charges. Adsorbed particles behave as ideal-gas particles in a one-dimensional box whose length corresponds to the parameter of stickiness. Among various scenarios considered are a single- and two-wall confinement as well as the case of sticky counterions capable of associating into pairs. Exact solutions provide a view of the role and behavior of surface charge fluctuations, which is an important step in the "beyond-mean-field" analysis. Consequently, the model serves as a simple paradigm of the mechanism that gives rise to the Kirkwood-Shumaker interactions detected in real systems.