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 () is the same as pure water at all concentrations. The second decay () is also the same as that of pure water at the lower concentrations, and then, it slows with increasing concentration. The slower dynamics ( and ), 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.