Structural Models and Molecular Thermodynamics of Hydration of Ions and Small Molecules

Solution equilibria are at the core of solvent-catalyzed reactions, solute separations, drug delivery, vapor partitioning and interfacial phenomena. Molecular simulation using thermodynamic integration or perturbation theory allows the calculation of these equilibria from parameterized force field models; however, the statistical many-body nature of solution environments inevitably complicates molecular interpretations of these phenomena. If our goal is molecular understanding in addition to prediction, then the statistical thermodynamic theories designed for mechanistic insight from structural analyses are especially important. In this report, we survey recent advances in the thermodynamic analysis of rigorous local structural models based on chemical structure. © 2012 Elsevier B.V.