Fast Structural Dynamics in Concentrated HCl Solutions: From Proton Hopping to the Bulk Viscosity.

Concentrated acid solutions, particularly HCl, have been studied extensively to examine the proton hopping and infrared spectral signatures of hydronium ions. Much less attention has been given to the structural dynamics of concentrated HCl solutions. Here, we apply optical heterodyne detected-optical Kerr effect (OHD-OKE) measurements to examine HCl concentration-dependent dynamics from moderate (0.8 m) to very high (15.5 m) concentrations and compare the results to the dynamics of NaCl solutions, as Na+ is similar in size to the hydronium cation. Both HCl and NaCl OHD-OKE signals decay as triexponentials at all concentrations, in contrast to pure water, which decays as a biexponential. Two remarkable features of the HCl dynamics are the following: (1) the bulk viscosity is linearly related to the slowest decay constant, t3, and (2) the concentration-dependent proton hopping times, determined by ab initio MD simulations and 2D IR chemical exchange experiments, both obtained from the literature, fall on the same line as the slowest structural dynamics relaxation time, t3, within experimental error. The structural dynamics of hydronium/chloride/water clusters, with relaxation times t3, are responsible for the concentration dependence of microscopic property of proton hopping and the macroscopic bulk viscosity. The slowest time constant (t3), which does not have a counterpart in pure water, is 3 ps at 0.8 m and increases by a factor of ∼2 by 15.5 m. The two fastest HCl decay constants, t1 and t2, are similar to those of pure water and increase mildly with the concentration.

Water-in-Salt: Fast Dynamics, Structure, Thermodynamics, and Bulk Properties.

We present concentration-dependent dynamics of highly concentrated LiBr solutions and LiCl temperature-dependent dynamics for two high concentrations and compare the results to those of prior LiCl concentration-dependent data. The dynamical data are obtained using ultrafast optical heterodyne-detected optical Kerr effect (OHD-OKE). The OHD-OKE decays are composed of two pairs of biexponentials, i.e., tetra-exponentials. The fastest decay (t1) is the same as pure water's at all concentrations within error, while the second component (t2) slows slightly with concentration. The slower components (t3 and t4), not present in pure water, slow substantially, and their contributions to the decays increase significantly with increasing concentration, similar to LiCl solutions. Simulations of LiCl solutions from the literature show that the slow components arise from large ion/water clusters, while the fast components are from ion/water structures that are not part of large clusters. Temperature-dependent studies (15-95 °C) of two high LiCl concentrations show that decreasing the temperature is equivalent to increasing the room temperature concentration. The LiBr and LiCl concentration dependences and the two LiCl concentrations' temperature dependences all have bulk viscosities that are linearly dependent on τcslow, the correlation time of the slow dynamics (weighted averages of t3 and t4). Remarkably, all four viscosity vs 1/τCslow plots fall on the same line. Application of transition state theory to the temperature-dependent data yields the activation enthalpies and entropies for the dynamics of the large ion/water clusters, which underpin the bulk viscosity.