Monte Carlo Simulation Methods for Computing Liquid–Vapor Saturation Properties of Model Systems

• DOI: 10.1021/ct400074p
• Publication Date: 2013-05-17T20:18:09Z
• Authors: Kaustubh S. Rane; Sabharish Murali; Jeffrey R. Errington
• Keywords: 0103 physical sciences; 01 natural sciences

We discuss molecular simulation methods for computing the phase coexistence properties of complex molecules. The strategies that we pursue are histogram-based approaches in which thermodynamic properties are related to relevant probability distributions. We first outline grand canonical and isothermal-isobaric methods for directly locating a saturation point at a given temperature. In the former case, we show how reservoir and growth expanded ensemble techniques can be used to facilitate the creation and insertion of complex molecules within a grand canonical simulation. We next focus on grand canonical and isothermal-isobaric temperature expanded ensemble techniques that provide a means to trace saturation lines over a wide range of temperatures. To demonstrate the utility of the strategies introduced here, we present phase coexistence data for a series of molecules, including n-octane, cyclohexane, water, 1-propanol, squalane, and pyrene. Overall, we find the direct grand canonical approach to be the most effective means to directly locate a coexistence point at a given temperature and the isothermal-isobaric temperature expanded ensemble scheme to provide the most effective means to follow a saturation curve to low temperature.