Dicyanamide Anion Reports on Water Induced Local Structural and Dynamic Heterogeneity in Ionic Liquid Mixtures

The effects of limited amounts (under 21.6% χ_Water) of water on 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF₄) and 1-butyl-3-methylimidazolium dicyanamide (BmimDCA) room-temperature ionic liquid (RTIL) mixtures were characterized by tracking changes in the linear and two-dimensional infrared (2D IR) vibrational features of the dicyanamide anion (DCA). Peak shifts with increasing water suggest the formation of water-associated and nonwater-associated DCA populations. Further results showed clear differences in the dynamic behavior of these different populations of DCA at low (defined here as below 2.5% χ_Water), mid (defined here as between 2.5% χ_Water and 9.6% χ_Water), and high (defined here as between 11.6% χ_Water and 21.6% χ_Water) range water concentrations. Vibrational relaxation is accelerated with increasing water content for water-associated populations of DCA, indicating water facilitates population relaxation, possibly through the provision of additional bath modes. Conversely, spectral diffusion of water-associated populations slowed dramatically with increasing water, suggesting that water drives the formation of distinct and noninterchangeable or very slowly interchangeable local solvent environments.