The effect of dilution on induced free charge density gradients in room temperature ionic liquids

We report on changes in the magnitude and length scale of the induced free charge density gradient, ρ_f, in three imidazolium room temperature ionic liquids (RTILs) with dilution by methanol and acetonitrile. Using depth- and time-resolved fluorescence measurements of cresyl violet rotational diffusion, we find that ρ_f persists in RTILs to varying degrees depending on RTIL and diluent identity, and in all cases the functional form of ρ_f is not a smooth monotonic diminution in either magnitude or persistence length with increasing diluent, but a stepwise collapse. This finding is consistent with changes in the bulk RTIL as a function of dilution seen using rotational diffusion measurements that show the rotating entity in bulk RTILs exhibits a larger effective hydrodynamic volume than would be expected based on bulk viscosity data for the diluted RTILs. This excess hydrodynamic volume can be understood in the context of aggregation of RTIL ion pairs in the diluted RTIL system. The size of the aggregates is seen to depend on RTIL identity and diluent, and in all cases aggregate size increases with increasing dilution. This finding is consistent with the ρ_f dependence on dilution data. The collapse of ρ_f is seen to correlate with the onset of RTIL ion pair dimer formation, a condition that may facilitate dissociated RTIL ion mobility in the binary system.