Finite size effects and optimization of the calculation of the surface tension in surfactant mixtures at liquid/vapour interfaces

Abstract: The surface tension of monolayers with mixtures of anionic and nonionic surfactant at the liquid/vapour interface is studied. Previous works have observed that calculations of the surface tension of simple fluids show artificial oscillations for small interfacial areas, indicating that the surface tension data fluctuate due to the finite size effects and periodic boundary conditions. In the case of simulations of monolayers composed of surfactant mixtures, the surface tension not only oscillates for small areas but can also give non-physical data, such as negative values. Analysis of the monolayers with different surfactant mixtures, ionic (DTAB, CTAB, SDS) and nonionic (SB3-12), was done for density profiles, parameters of order and pair correlation functions for small and large box areas and all of them present similar behaviour. The fluctuations and the non-physical values of the surface tension are corrected when boxes with large interfacial areas are considered. The results indicate that in order to obtain reliable values of the surface tension, in computer simulations, it is important to choose not only the correct force field but also the appropriate size of the simulation box.