Modeling nonionic aqueous solutions: the acetone-water mixture.

Abstract

Several combinations of existing classical water and acetone models are studied by molecular dynamic simulations in order to sort out which models can reproduce available experimental data: enthalpies, pressure, densities, diffusion coefficients, and Kirkwood-Buff integrals. It turns out that all these properties, but the last, are rather well reproduced by all models, and with little numerical effort. By contrast, trials to measure by simulations the Kirkwood-Buff integrals lead to very long simulation times, thus revealing unexpected divergent behavior between the different models, such as phase separation, for example, and ultimately leading to a failure of any models combinations to reproduce these properties according to the experimental tendencies. It is argued herein that these deficiencies provide, in fact, an insightful picture of the microscopic structure of the solution, particularly into the relation between the hydrogen-bond network and the concentration fluctuations, as well as the role played by the solute in their spatial organization.