Significance: Many important biological and industrial processes, ranging from protein folding and ligand binding to self-assembly of materials at interfaces, take place in solution and are mediated by driving forces rooted in solvation. However, conceptual and computational difficulties arising from long-ranged Coulomb interactions still present a challenge to current approaches. Here we present a framework to determine very accurately the long-ranged contributions to solvation free energies in charged and polar systems from models with only short-ranged, local interactions. We examine a variety of ubiquitous solvation processes, including hydrophobic and ionic hydration, as well as colloidal overcharging. The theory additionally suggests ways to improve density functional theories of solvation by providing insights into commonly used approximations.

Molten chloride salt is recognized as a promising heat transfer and storage medium in concentrating solar power in recent years, but there is a serious lack for thermal property data of molten chloride salts. In this work, local structures and thermal properties for molten chloride salt—including NaCl, MgCl₂, and ZnCl₂—were precisely simulated by Born–Mayer–Huggins (BMH) potential in a rigid ion model (RIM) and a polarizable ion model (PIM). Compared with experimental data, distances between cations, densities, and heat capacities of molten chloride slats calculated from PIM agree remarkably better than those from RIM. The polarization effect brings an extra contribution to screen large repulsive Coulombic interaction of cation–cation, and then it makes shorter distance between cations, larger density and lower heat capacity. For NaCl, MgCl₂, and ZnCl₂, PIM simulation deviations of distances between cations are respectively 3.8%, 3.7%, and 0.3%. The deviations of density and heat capacity for NaCl between PIM simulation and experiments are only 0.6% and 2.2%, and those for MgCl₂ and ZnCl₂ are 0.7–10.7%. As the temperature rises, the distance between cations increases and the structure turns into loose state, so the density and thermal conductivity decrease, while the ionic self-diffusion coefficient increases, which also agree well with the experimental results.