Capillary Waves at Liquid/Vapor Interfaces: A Molecular Dynamics Simulation

Abstract

Evidence for capillary waves at a liquid/vapor interface are presented from extensive molecular dynamics simulations of a system containing up to 1.24 million Lennard-Jones particles. Careful measurements show that the total interfacial width depends logarithmically on $L_\parallel$, the length of the simulation cell parallel to the interface, as predicted theoretically. The strength of the divergence of the interfacial width on $L_\parallel$ depends inversely on the surface tension $γ$. This allows us to measure $γ$ two ways since $γ$ can also be obtained from the difference in the pressure parallel and perpendicular to the interface. These two independent measures of $γ$ agree provided that the interfacial order parameter profile is fit to an error function and not a hyperbolic tangent, as often assumed. We explore why these two common fitting functions give different results for $γ$.