Classical van der Waals interactions between spherical bodies of dipolar fluid

Abstract

The van der Waals interaction free energy A(int) between two spherical bodies of Stockmayer fluid across a vacuum is calculated using molecular simulations and classical perturbation theory. The results are decomposed into their electrostatic and Lennard-Jones parts, and the former is shown to agree excellently with predictions from dielectric continuum theory. A(int) is decomposed into its energetic and entropic contributions and the results are compared with analytical predictions. Finally, we expand the electrostatic part of A(int) in a multipole expansion, and show that the surprisingly good agreement between the molecular and continuum descriptions is likely due to a cancellation of errors coming from the neglect of the discrete nature of the fluid within the dielectric description.