Hard sphere cavity in a Lennard-Jones liquid

A Lennard-Jones (6-12)liquid containing a single, immobile hard sphere cavity is studied by molecular dynamics simulation. The cavity radii range from infinity (hard wall) to 0.5σ. Number densities, Irving–Kirkwood normal pressure, force, and self-energy are reported. The particle number density extrapolated up to the cavity wall, as well as statistics of empty space around the cavity are used to extract the chemical potential of the cavity and other quantities as functions of cavity radius at constant temperature and far-away pressure (density) of the solvent. Extrapolation from macroscopic down to molecular cavity sizes greater than σ is discussed.