Theoretical study of the effect of π^{+}-π^{+} association in imidazolium ionic liquids at charged interfaces

We develop an extended classical density-functional theory to describe clustering of imidazolium-based cations into linear chains, driven by π-π stacking. We find that the associating system displays a similar short-ranged structure to the completely dissociated fluid. We also construct a restricted primitive model for associating ionic species in an RTIL+solvent mixture. The double-layer formed in these systems exhibits strong overscreening by the cation chains, as expected. Significantly enhanced capacitance is also observed for the case where counterions are the associating species. The established density-functional method can be also used to describe polydisperse polyelectrolyte models.