Determination of surface tension in binary mixtures using transition-matrix Monte Carlo.

Physical and Chemical Properties Division, National Institute of Standards and Technology, 100 Bureau Drive MS 8380, Gaithersburg, Maryland 20899-8380, USA. vincent.shen@nist.gov

We present a methodology based on grand-canonical transition-matrix Monte Carlo and finite-size scaling analysis to calculate surface tensions in binary mixtures. In particular, mixture transition-matrix Monte Carlo is first used to calculate apparent, system-size-dependent free-energy barriers separating coexisting fluid phases. Finite-size scaling is then used to extrapolate these values to the infinitely large system limit to determine the true thermodynamic surface tension. A key distinction of the methodology is that it yields the entire isothermal surface-tension curve for a binary mixture in a relatively small number of simulations. We demonstrate the utility of the method by calculating surface-tension curves for three binary Lennard-Jones mixtures. While we have only examined the surface tension of simple fluids in this work, the method is general and can be extended to molecular fluids as well as to determine interfacial tensions of liquid-liquid interfaces.

PMID: 16422640 [PubMed]