Calculation of phase coexistence properties and surface tensions of n-alkanes with grand-canonical transition-matrix monte carlo simulation and finite-size scaling.
Grand-canonical transition-matrix Monte Carlo is combined with configurational-bias and expanded ensemble Monte Carlo techniques to obtain saturated densities and vapor pressures of select n-alkanes. Surface tension values for butane, hexane, and octane are also computed via the finite-size scaling method of Binder. The exponential-6 model of Errington and Panagiotopoulos is used to describe the molecular interactions. The effect of the number of configurational-bias trial conformations on the efficiency of phase equilibra calculations is studied. We find that a broad range of trial conformation numbers give reasonable performance, with the optimal value increasing with decreasing temperature for a fixed chain length. Phase coexistence properties are in good agreement with literature values and are obtained with very reasonable computing resources. Similar to other recently developed n-alkane force fields, the exponential-6 model overestimates the surface tension relative to experimental values. Statistical uncertainties for coexistence properties obtained with the current approach are relatively small compared to existing methods.
Singh
Jayant K
JK
Department of Chemical and Biological Engineering, University at Buffalo, The State University of New York, Buffalo, New York 14260-4200, USA.
Errington
Jeffrey R
JR
D000473:Alkanes / Q000737:chemistry*; D003198:Computer Simulation; D008567:Membranes, Artificial; D008956:Models, Chemical; D009010:Monte Carlo Method; D044367:Phase Transition; D013500:Surface Tension
D000473:Alkanes; D008567:Membranes, Artificial