The Effect of Model Internal Flexibility Upon NEMD Simulations of Viscosity

Abstract

The influence of model flexibility upon simulated viscosity was investigated. Nonequilibrium molecular dynamics (NEMD) simulations of viscosity were performed on seven pure fluids using three models for each: one with rigid bonds and angles, one with flexible angles and rigid bonds, and one with flexible bonds and angles. Three nonpolar fluids (propane, n-butane, and isobutane), two moderately polar fluids (propyl chloride and acetone), and two strongly polar fluids (methanol and water) were studied. Internal flexibility had little effect upon the simulated viscosity of nonpolar fluids. While model flexibility did affect the simulated viscosity of the polar fluids, it did so principally by allowing a density-dependent change in the dipole moment of the fluid. By using a rigid model with the same geometry and dipole moment as the average flexible molecule at the same density, it was shown that the direct effect of flexibility is small even in polar fluids. It was concluded that internal model flexibility does not enhance the accuracy of viscosities obtained from NEMD simulations as long as the appropriate model geometry is used in the rigid model for the desired simulation density.