Effect of torsional potential on the predicted phase behavior of n-alkanes

Abstract

The effect of torsional potential on the predictions of simulation for vapor–liquid equilibria of n-alkanes is determined. Calculations are performed with histogram-reweighting Monte Carlo simulations in the grand canonical ensemble. Decreasing the magnitude of energy barriers to dihedral rotation or allowing free rotation is found to have no effect on the predicted vapor–liquid equilibria. Restriction of the dihedral angles to a Gaussian distribution around the minimum energy conformation causes an under-prediction of the liquid densities and critical temperatures by a maximum of 7% and 2%, respectively, with discrepancies increasing monotonically with the number of dihedral angles present in a molecule. No significant deviation in vapor pressure is observed for any compound, regardless of torsional potential used. An analysis of the conformational behavior reveals that restriction of the dihedral sampling has a measurable effect on excluded volume of the molecule, and this change of conformational behavior is responsible for the reduction in the predicted saturated liquid densities observed in this work. Similar calculations for force fields employing reduced dihedral potentials or freely jointed chains show little change in the predicted excluded volume compared to the reference force field.