Surface tension and long range corrections of cylindrical interfaces.

Abstract

The calculation of the surface tension of curved interfaces has been deeply investigated from molecular simulation during this last past decade. Recently, the thermodynamic Test-Area (TA) approach has been extended to the calculation of surface tension of curved interfaces. In the case of the cylindrical vapour-liquid interfaces of water and Lennard-Jones fluids, it was shown that the surface tension was independent of the curvature of the interface. In addition, the surface tension of the cylindrical interface is higher than that of the planar interface. Molecular simulations of cylindrical interfaces have been so far performed (i) by using a shifted potential, (ii) by means of large cutoff without periodic boundary conditions, or (iii) by ignoring the long range corrections to the surface tension due to the difficulty to estimate them. Indeed, unlike the planar interfaces there are no available operational expressions to consider the tail corrections to the surface tension of cylindrical interfaces. We propose here to develop the long range corrections of the surface tension for cylindrical interfaces by using the non-exponential TA (TA2) method. We also extend the formulation of the Mecke-Winkelmann corrections initially developed for planar surfaces to cylindrical interfaces. We complete this study by the calculation of the surface tension of cylindrical surfaces of liquid tin and copper using the embedded atom model potentials.