Vapor−Liquid Interface of the Lennard-Jones Truncated and Shifted Fluid: Comparison of Molecular Simulation, Density Gradient Theory, and Density Functional Theory

Abstract

The vapor–liquid interface of the Lennard-Jones truncated and shifted (LJTS) fluid with a cutoff radius of 2.5σ is investigated for temperatures covering the range between the triple point and the critical point. Three different approaches to model the vapor–liquid interface are used: molecular dynamics (MD) simulation, density gradient theory (DGT), and density functional theory (DFT). The surface tension, pressure, and density profiles, including the oscillatory layering structure of the fluid at the interface, are investigated. The PeTS (Perturbed Truncated and Shifted) equation of state and PeTS-interfacial functional, based on perturbation theory, are used to calculate the Helmholtz free energy in the DGT and DFT approach. They are consistent with the LJTS force field model. Overall, both DGT and DFT describe the results from computer experiments well. An oscillatory layering structure is found in MD and DFT.