Dynamics of Concentrated Aqueous Lithium Chloride Solutions Investigated with Optical Kerr Effect Experiments.

We report the dynamics of concentrated lithium chloride aqueous solutions over a range of moderate to high concentrations. Concentrations (1-29 to 1-3.3 LiCl-water) were studied in which, at the highest concentrations, there are far too few water molecules to solvate the ions. The measurements were made with optically heterodyne-detected optical Kerr effect experiments, a non-resonant technique able to observe dynamics over a wide range of time scales and signal amplitudes. While the pure water decay is a biexponential, the LiCl-water decays are tetra-exponentials at all concentrations. The faster two decays arise from water dynamics, while the slower two decays reflect the dynamics of the ion-water network. The fastest decay ( t 1 ) is the same as pure water at all concentrations. The second decay ( t 2 ) is also the same as that of pure water at the lower concentrations, and then, it slows with increasing concentration. The slower dynamics ( t 3 and t 4 ), which do not have counterparts in pure water, arise from ion-water complexes and, at the highest concentrations, an extended ion-water network. Comparisons are made between the concentration dependence of the observed dynamics and simulations of structural changes from the literature, which enable the assignment of dynamics to specific ion-water structures. The concentration dependences of the bulk viscosity and the ion-water network dynamics are directly correlated. The correlation provides an atomistic-level understanding of the viscosity.