(111b) Field Biased Molecular Simulation Technique for Complex Fluids

Field-biased molecular simulation technique has been implemented to characterize TraPPE[1] database and fill the gap between continuous and discontinuous potentials. In this way thermodynamic perturbation theory (TPT)[2] can be used for both continuous and discontinuous potentials and only the reference part needs to be simulated. For long-range interaction PPPM[3] method and its alternatives[4] has been implemented into the force field and the charges has been assigned according to Siepmann et al.[5] It is not necessary to update the Coulombic interactions after each timestep and the guideline for this update is after each 10,000 collisions. In this way, we create a time and space coarse-grained multiscale molecular simulation method that is able to handle thermodynamics[6, 7], interfacial[8-12] and transport properties[13] in a similar fashion.

1. Chen, B.; Potoff, J. J.; Siepmann, J. I., Monte Carlo calculations for alcohols and their mixtures with alkanes. Transferable potentials for phase equilibria. 5. United-atom description of primary, secondary, and tertiary alcohols. J. Phys. Chem. B. 2001, 105, (15), 3093-3104. 2. Barker, J. A.; Henderson, D., Perturbation Theory and Equation of State for Fluids. II. Successful Theory of Liquids. J. Chem. Phys. 1967, 47, 4714. 3. Frenkel, D.; Smit, B., Understanding Molecular Simulation: From Algorithms to Applications. 2nd ed.; Academic Press: San Diego, 2002. 4. Fennell, C. J.; Gezelter, J. D., Is the Ewald summation still necessary? Pairwise alternatives to the accepted standard for long-range electrostatics. Journal of Chemical Physics 2006, 124, (23). 5. Siepmann, J. I., Inferring intermolecular potential models from quantum mechanics and experiment. Ind. Eng. Chem. Res. 2009, 2009, in press. 6. Elliott, J. R.; Vahid, A., Field-Biased Molecular Simulation Methods for Hard Sphere Polymer Chains. In AIChE Annual Meeting, Nashville, TN, 2009. 7. Vahid, A.; Elliott, J. R., Transferable Intermolecular Potentials for Carboxylic Acids and Their Phase Behavior. Aiche Journal 2010, 56, (2), 485-505. 8. Wardle, K. E.; Carlson, E.; Henderson, D.; Rowley, R. L., Molecular-dynamics simulation of the effect of ions on a liquid-liquid interface for a partially miscible mixture. Journal of Chemical Physics 2004, 120, (16), 7681-7688. 9. Wardle, K. E.; Henderson, D.; Rowley, R. L., Molecular dynamics simulation of surfactant effects on ion transport through a liquid-liquid interface between partially miscible liquids. Fluid Phase Equilibria 2005, 233, (1), 96-102. 10. Hansen, J.-P.; McDonald, I. R., Theory of Simple Liquids. 3 rd ed.; Academic Press: Amsterdam, 2006. 11. Fredrickson, G. H., The Equilibrium Theory of Inhomogeneous Polymers. 1st ed.; Oxford University Press: New York, 2006. 12. Henderson, D., Fundamentals of Inhomogeneous Fluids. Marcel-Dekker: New York, 1992. 13. Öttinger, H. C., Beyond Equilibrium Thermodynamics 1st ed.; John Wilcy & Sons: New Jersey, 2005.