Dynamics in an Idealized Ionic Liquid Model

Abstract

An idealized four-site ionic liquid model having characteristics approximating those of 1-butyl-3-methylimidazolium hexafluorophosphate ([Im(41)][PF(6)]) is introduced as a low-cost alternative to existing all-atom models for purposes of simulating solute-based dynamics over nanosecond and longer time scales. The structural and energetic properties of the model are in reasonable agreement with those of [Im(41)][PF(6)] and similar ionic liquids, but the dynamics are unrealistically slow. A temperature shift of approximately 100 K is required to produce agreement between the viscosity and diffusion coefficients of the model and experimental values. Several aspects of the ion dynamics such as subdiffusive translational motions, non-Gaussian van Hove distributions, and jumplike displacements in both positions and orientations, are similar to behavior observed in supercooled liquids. Translational diffusion coefficients and rotational correlation times show roughly the proportionalities to viscosity expected from hydrodynamic models, and slip hydrodynamic calculations provide reasonable accuracy in some cases. But anomalously high rotational diffusion coefficients which decouple from viscosity at low temperature are also observed. These anomalies are explained in terms of the prevalence of 180 degrees rotational jumps coupled to the presence of marked heterogeneity in rotational motions, especially about one molecular axis. Comparisons between the dynamics observed in the ionic liquid (IL) model and a neutral mixture (NM) counterpart help to explain the origins of the distinctive dynamics in ionic liquids compared to conventional solvents. The requirement for balancing electrostatic interactions in the IL leads to uniform and interleaved distributions of cations and anions resembling a distorted ionic lattice, similar to the structure of molten NaCl. The resistance to reorganizing this structure is what leads to the slow dynamics of ionic liquids. The coupling among large collections of ions is presumably responsible for the similarity of ionic liquids to supercooled conventional liquids.