(68e) Blowing Bubbles in Lennard-Jonesium along the Saturation Curve

Solvation plays a crucial role in multi-scale processes from gas solubility, to the mesoscopic organization of self-assembled structures, to macroscopic phase separation. We have performed extensive molecular simulations of the Lennard-Jones fluid to determine its liquid-vapor coexistence properties, and solvent contact densities with cavity solutes up to 10 times the diameter of the solvent from the triple point to the critical point. These simulations are analyzed using a revised scaled-particle theory to evaluate the thermodynamics of cavity solvation and curvature dependent interfacial properties along the saturation curve. While the thermodynamic signatures of cavity solvation are distinct from those in water, exhibiting a chemical potential dominated by a large temperature independent enthalpy, the solvent dewets cavities of increasing size similar with water near coexistence. The interfacial tension for forming a liquid-wall interface is found to be consistently greater than the liquid-vapor surface tension of the Lennard-Jones fluid by up to 10%, and potentially reflects the suppression of high amplitude fluctuations at the cavity surface. The first-order curvature correction for the surface tension is negative and appears to diverge to negative infinity at temperatures approaching the critical point. Our results point to the success of the revised scaled-particle theory at bridging molecular and macroscopic descriptions of cavity solvation.