Monte Carlo Simulations of Fluids: Microheterogeneity and Electric Field Effects.

摘要

In recent years, molecular simulations aimed at predicting thermophysical properties and uncovering new phenomena of chemical systems have become an increasingly important area of research. The present work begins with an introduction to statistical mechanics and molecular simulation methods, followed by a more in depth discussion of specialized Monte Carlo techniques. Chapter 1 ends with a section on force fields, specifically the transferable potentials for phase equilbria (TraPPE) force field. In Chapter 2, the extenstion of the TraPPE-UA force field to acrylate monomers is presented. A discussion of the parameterization strategy is followed by the results for both single-component systems and binary mixtures. Chapter 3 examines binary mixtures of nitrotoluene isomers with n-decane, starting with dielectric properties, then moving on to a discussion of microheterogeneity and the effects of the electric field. In Chapter 4 the effect of an electric field on the vapor-liquid equilibria of three small polar molecules is presented. The resulting phase equililbrium behavior is presented first, followed by a discussion of the structural and energetic properties of these systems. Chapter 5 introduces the TraPPE coarse-grain model for linear alkanes. A discussion of the parameterization strategy is followed by the results for single component systems and a binary mixture. In Chapter 6 the accuracy of combining TraPPE-EH parameters for aromatic rings with UA parameters for alkyl and vinyl substituents is tested.