Density functional theory of confined ionic liquids: the influence of power-law attractions on molecule distributions and surface forces

Abstract

Interaction energies and density profiles for two model ionic liquids, [C₄mim⁺][BF₄⁻] and [C₄mim⁺][TFSI⁻], confined between charged planar walls are studied within a density functional theory framework. The results of these simulations are also compared with results assuming a simpler linear hexamer–monomer, cation–anion system. We focus attention on the effect on the atom site distributions and the surface forces of an additional, specific attractive potential between oppositely charged molecules. We consider both short- and long-ranged attractive potentials in order to span the degree to which the ionic counterions associate. Independent of its strength, we interpret the results found with the short-ranged potential to be a manifestation of limited molecular association. In contrast, depending on its strength, the results found with the long-ranged potential suggest a much stronger and possibly longer ranged associations of ionic groups. Both potentials are found to influence the behavior of the surface force at small separations, while the long-ranged attractive potential has the greater influence of the two on the long-ranged behavior of the surface force.