Effects of Salts on the Solvation of Hydrophobic Objects in Water

The solvation of large, hydrophobic objects in water is facilitated by the formation of a low-density region surrounding the solute that is separated from the bulk liquid by an interface, which has a structure that resembles that between a liquid and its vapor. We study the effect of dissolved sodium chloride on the thermodynamics of solvation and on the solvent structure surrounding hydrophobic solutes in the size regime where this interface is not yet fully formed. Using biased Molecular Dynamics computer simulations, we calculate solvation free energies and orientational distributions of water molecules at different salt concentrations and solute sizes. We find that while the effects of sodium chloride on thermodynamic properties are small, the ions' response to the presence of a hydrophobic solute differs significantly from that of the water. Our findings provide mechanistic insight into how our understanding of hydrophobic solvation in water can be extended to electrolyte solutions.