Translational Diffusion in a Set of Imidazolium-Based Ionic Liquids [bmim]⁺A^- and Their Mixtures with Water

As the development of the work (J. Phys. Chem. B 2019, 123 (10), 2362-2372), we have investigated the translational mobility in the same set of dried imidazolium-based ionic liquids (ILs) [bmim]A (A = BF₄^-, NO₃^-, TfO^-, I^-, Br^-, and Cl^-) in a wide temperature range using the NMR technique. It is shown that for the [bmim]⁺ cation, the temperature dependencies of product Dη do not follow the Stokes-Einstein relation for most systems studied, that is, the so-called "diffusion-viscosity decoupling" was realized. The correlation between local and translational mobility in pure IL of the [bmim][A] type was investigated using the data on NMR relaxation rates and diffusion coefficients. The most recent hypothesis of "water pockets" in mixtures of IL with water is critically discussed. Considering the totality of data in the literature and obtained here, we propose a specific model of the microstructure which may be applied up to water concentrations of 80-90 mol % (the structure of water-rich solutions is out of our current consideration). To confirm the model, molecular dynamics simulations of "IL-water" mixtures were also carried out.