Transferability of Local Density-Assisted Implicit Solvation Models for Homogeneous Fluid Mixtures.

The application of bottom-up coarse grained (CG) models to study the equilibrium mixing behavior of liquids is rather challenging, since these models can be significantly influenced by the density or the concentration of the state chosen during parametrization. This dependency leads to low transferability in density/concentration space and has been one of the major limitations in bottom-up coarse graining. Recent approaches proposed to tackle this shortcoming range from the addition of thermodynamic constraints, to an extended ensemble parametrization, to the addition of supplementary terms to the system's Hamiltonian. To study fluid phase equilibria with bottom-up CG models, the application of local density (LD) potentials appears to be a promising approach, as shown in previous work by Sanyal and Shell [T. Sanyal, M. S. Shell, J. Phys. Chem. B, 2018, 122, 5678]. Here, we want to further explore this method and test its ability to model a system which contains structural inhomogeneities only on the molecular scale, namely, solutions of methanol and water. We find that a water-water LD potential improves the transferability of an implicit-methanol CG model toward high water concentration. Conversely, a methanol-methanol LD potential does not significantly improve the transferability of an implicit-water CG model toward high methanol concentration. These differences appear due to the presence of cooperative interactions in water at high concentrations that the LD potentials can capture. In addition, we compare two different approaches to derive our CG models, namely, relative entropy optimization and the Inverse Monte Carlo method, and formally demonstrate under which analytical and numerical assumptions these two methods yield equivalent results.