Oscillatory surface tension due to finite-size effects

摘要

The simulation results of surface tension at the liquid-vapor interface are presented for fluids interacting with Lennard Jones and square-well potentials.From the simulation of liquids we have reported [M.Gonzalez-Melchor et al,J.Chem.Phys.122,4503 (2005)] that the components of pressure tensor in parallelepiped boxes are not the same when periodic boundary conditions and small transversal areas are used.This fact creates an artificial oscillatory stress anisotropy in the system with even negative values.By doing direct simulations of interfaces we show in this work that surface tension has also an oscillatory decay at small surface areas;this behavior is opposite to the monotonic decay reported previously for the Lennard Jones fluid.It is shown that for small surface areas,the surface tension of the square-well potential artificially takes negative values and even increases with temperature.The calculated surface tension using a direct simulation of interfaces might have two contributions:one from finite-size effects of interfacial areas due to box geometry and another from the interface.Thus,it is difficult to evaluate the true surface tension of an interface when small surface areas are used.Care has to be taken to use the direct simulation method of interfaces to evaluate the predicted surface tension as a function of interfacial area from capillary-wave theory.The oscillations of surface tension decay faster at temperatures close to the critical point.It is also discussed that a surface area does not show any important effect on coexisting densities,making this method reliable to calculate bulk coexisting properties using small systems.