Putting the squeeze on cavities in liquids: Quantifying pressure effects on solvation using simulations and...

Extensive molecular simulations of the Lennard-Jones fluid are performed to examine the response of the excess chemical potential of cavitylike solutes to applied pressure. Solutes as large as ten times the solvent diameter are considered. The simulations are analyzed using the revised scaled-particle theory developed by Ashbaugh and Pratt to evaluate the thermodynamics of cavity solvation and curvature dependent interfacial properties well into the compressed liquid portion of the solvent phase diagram. The revised theory provides a quantitatively accurate description of the solvent-solute contact correlation function for all solutes and state points considered. The main structural effect of increasing pressure is to push the solvent molecules up against the solute surfaces, counteracting the dewetting that is observed at lower pressures along the solvent saturation curve. Decomposing the excess chemical potential of cavities into volume and surface-area contributions shows that pressure differentially affects the interfacial free energies of molecular versus macroscopic solutes. The interfacial free energy of surfaces of molecular dimension monotonically decreases with applied pressure, while that of surfaces larger than a small cluster of solvent molecules exhibit a maximum with increasing pressure, which may play a role in pressure-induced disaggregation of molecular assemblies. Moreover, since the pressure dependence of the interfacial free energy is thermodynamically linked to the excess adsorption of solvent on the solute surface, the former is potentially a measurable macroscopic indicator of microscopic wetting∕dewetting phenomena, implicated in hydrophobic interactions between macroscopic hydrophobic particles. Finally, some inferences about pressure-dependent solvation processes in water are made by using the revised theory to analyze previously published simulation data.