Pair correlations that link the hydrophobic and Hofmeister effects

The Hofmeister effect describes how different ions make solutes more or less hydrophobic. The effect is thought to occur due to structural changes in the solvent induced by the ion's presence, particularly in water. In this study, the structural changes in water due to the presence of ions are investigated by molecular dynamics simulations of various monatomic ions in the SPC/E water model. Structural analyses reveal specific orientations of solvating waters around each of the ions studied. Using a new method, these orientations are quantified by a set of pair correlation functions that describe dipole–ion correlations in structure. These correlations are shown to contribute to the potential of mean force between waters and the ion of interest, and therefore to the free energy of the system. The magnitude of this free energy is found to result in a Hofmeister series for the various ions studied, therefore demonstrating a Hofmeister effect with respect to water's structure that is quantified by pair correlation functions. Most crucially, the pair correlations that lead to this Hofmeister effect also contribute to the hydrophobic effect (the entropy of hydrophobic solvation) [Liu et al., J. Chem. Phys., 2015, 142, 114117], and those which dominate the hydrophobic effect are modulated by an ion's presence, therefore demonstrating a mechanistic link between the two effects.