Interfacial properties of the Mie n−6 fluid: Molecular simulations and gradient theory results

Abstract

In a first part, interfacial properties of a pure monoatomic fluid interacting through the Mie n-6 potential (n=8, 10, 12, and 20) have been studied using extensive molecular simulations. Monte Carlo and molecular dynamics simulations have been employed, using, respectively, the test area approach and the mechanic route. In order to yield reference values, simulations have been performed with a cutoff radius equal to 10sigma, which is shown to be sufficient to avoid long range corrections. It is shown that both approaches provide results consistent with each other. Using the molecular simulations results, it is demonstrated that a unique scaling law is able to provide an accurate estimation of the surface tension whatever the repulsive exponent n, even far from the critical point. Furthermore, it is shown that the surface tension of the Mie n-6 fluid is as well accurately described by a unique Parachor's law. Density profiles are shown to be well represented by the tanh mean field profile, with slight deviations for the lowest temperatures and the smallest n. In addition, the interfacial width is shown to increase when n decreases (for a given reduced temperature) and to follow the usual scaling behavior for not too low temperature. In a second part, interfacial properties of the Mie n-6 fluid computed by the gradient theory, coupled with an equation of state based on the Barker-Henderson perturbation theory, have been compared with those obtained by molecular simulations. It is demonstrated that, even far from the critical point, the gradient theory is efficient to compute surface tensions and density profiles of this model fluid, provided the equation of state accurately model the phase behavior of the fluid involved (which is not the case for n=8 in this study).