Incorporation of ion and solvent structure into mean-field modeling of the electric double layer

An electric double layer forms when the small mobile ions of an electrolyte interact with an extended charged object, a macroion. The competition between electrostatic attraction and translational entropy loss of the small ions results in a diffuse layer of partially immobilized ions in the vicinity of the macroion. Modeling structure and energy of the electric double layer has a long history that has lead to the classical Poisson-Boltzmann theory and numerous extensions that account for ion-ion correlations and structural ion and solvent properties. The present review focuses on approaches that instead of going beyond the mean-field character of Poisson-Boltzmann theory introduce structural details of the ions and the solvent into the Poisson-Boltzmann modeling framework. The former include not only excluded volume effects but also the presence of charge distributions on individual ions, spatially extended ions, and internal ionic degrees of freedom. The latter treat the solvent either explicitly as interacting Langevin dipoles or in the form of effective non-electrostatic interactions, in particular Yukawa interactions, that are added to the Coulomb potential. We discuss how various theoretical models predict structural properties of the electric double layer such as the differential capacitance and compare some of these predictions with computer simulations.