Atomistic molecular dynamics simulations have been performed to investigate volumetric quantities and dynamic properties of binary trihexyltetradecylphosphonium bis(oxalato)-borate ([P-6,P-6,P-6,P-14][BOB]) ionic liquid (IL)/water mixtures with different water concentrations. The predicted liquid densities for typical [P-6,P-6,P-6,P-14][BOB] IL/water mixtures are consistent with available experimental data with a relative discrepancy of less than 3%. The liquid densities and excess molar volumes of all studied [P-6,P-6,P-6,P-14][BOB] IL/water mixtures are characterized by concave and convex features, respectively, within full water concentration range. The dynamic properties of [P-6,P-6,P-6,P-14] cations, [BOB] anions, and water molecules are particularly analyzed through calculation of velocity autocorrelation functions, diffusion coefficients, and reorientational autocorrelation functions and correlation times. The translational and reorientational mobilities of three species become faster upon increasing water concentration in [P-6,P-6,P-6,P-14][BOB] IL/water mixtures and present complex dynamical characteristics arising from three distinct microscopic diffusion features within the full water concentration range. The obtained striking volumetric quantities and particular dynamic properties are well correlated to microscopic liquid structural organization and distinct local ionic environment of all studied [P-6,P-6,P-6,P-14][BOB] IL/water mixtures.
2016. Vol. 120, no 30, 7446-7455 p.