Application of density functional theory to study the double layer of an electrolyte with an explicit dimer model for the solvent.

Most theoretical studies of an electrical double layer, which is formed by an electrolyte in contact with a charged electrode, employ a primitive model in which the solvent is represented by a dielectric continuum. This implicit-solvent model is convenient because computations are comparatively simple. However, it suppresses oscillations in the density profiles of ionic species that result from the discreteness of the solvent molecules. Furthermore, the implicit-solvent model yields poor results for the capacitance. In comparison with experiment at fixed electrode charge density, it predicts a too small electrode potential, and the resultant capacitance is too large. This latter discrepancy can be compensated in part by postulating the existence of an often fictitious inner layer whose properties are parametrized to agree best with experiment. The use of an implicit solvent model and an inner layer helps in correlating experimental results but rests on a faulty microscopic picture. Unfortunately, explicit consideration of solvent molecules poses both theoretical and numerical difficulties and, as a result, studies using an explicit solvent model have been few and far between. In this study, we consider a simple nonprimitive or explicit solvent model in which each solvent molecule is represented by a dimer composed of touching positive and negative hard spheres, with a resulting dipole moment that is equal to that of a water molecule, and the ions are represented by charged hard spheres. The density profiles and charge-potential relationship of this model are examined using the classical density functional theory. We find that the introduction of an explicit solvent increases the electrode potential, at fixed electrode charge, without the need to postulate a parametrized inner layer. Because of the solvent polarity, the ion profiles become strong oscillatory and show local charge inversion near a highly charged electrode surface at all ion concentrations.