Do Electrostatics Control the Diffusive Dynamics of Solitary Water? NMR and MD Studies of Water Translation and Rotation in Dipolar and Ionic Solvents

Abstract

NMR-based measurements of the diffusion coefficients and rotation times of solitary water and benzene at 300 K are reported in a diverse collection of 13 conventional organic solvents and 10 imidazolium ionic liquids. Proton chemical shifts of water are found to be correlated to water OH-stretching frequencies, confirming the importance of electrostatic interactions in these shifts. However, the influence of magnetic interactions in aromatic solvents renders chemical shifts a less reliable indicator of electrostatics. Diffusion coefficients (DB) and rotational correlation times (tB) of benzene in the solvents examined are accurately described as functions of viscosity (.) by DB..-0.81 and tB..0.64. Literature values of DB and tB in alkane and normal alcohols, which were not included among the solvents studied here, are systematically faster than predicted by these correlations, indicating that factors beyond solvent viscosity play a role in determining the friction on benzene. In contrast to benzene, water diffusion and rotation are poorly described in terms of viscosity alone, even in the dipolar and ionic solvents measured here. The present data and the substantial literature data already available on dilute water diffusion show a systematic dependence of DW on solvent polarity among isoviscous solvents. The aspect of solvent polarity most relevant to water dynamics is the ability of a solvent to accept hydrogen bonds from water, as conveniently quantified by the frequency of water's OH stretching band,..OH. The friction on translation,.tr = kBT/DW, and rotation,.rot = kBTtW, are both well correlated by functions of the form.(.,..OH) = a1.a2 exp (a3..OH), where the ai are adjustable parameters. Molecular dynamics simulations reveal a strong coupling between electrostatic and nonelectrostatic water-solvent interactions, which makes it impossible to dissect the friction on water into additive dielectric and hydrodynamic components. Simulations also provide a tentative explanation for the unusual form of the correlating function.(.,..OH), at least in the case of.rot.