Extended Charge-On-Particle Optimized Potentials for Liquid Simulation Acetone Model: The Case of Acetone–Water Mixtures

It is well-known that classical molecular dynamics simulations of acetone-water mixtures lead to a strong phase separation when using most of the standard all-atom force fields, despite the well-known experimental fact that acetone is miscible with water in any proportion at room temperature. We describe here the use of a charge-on-particle model for accounting for the induced polarization effect in acetone-water mixtures which can solve the demixing problem at all acetone molar fractions. The polarizability effect is introduced by means of a virtual site (VS) on the carbonyl group of the acetone molecule, which increases its dipole moment and leads to a better affinity with water molecules. The VS parameter is set by fitting the density of the mixture at different acetone molar fractions. The main novelty of the VS approach lies on the transferability and universality of the model because the polarizability can be controlled without modifying the force field adopted, like previous efforts did. The results are satisfactory also in terms of the transport properties, that is, diffusivity and viscosity coefficients of the mixture.