Keywords

molecular dynamics, fluid viscosity, molecular velocities

Abstract

Nonequilibrium molecular dynamics (NEMD) viscosity simulations of branched and linear alkanes at liquid densities were performed using both united-atom (UA) and all-atom (AA) intermolecular potential models in order to study the relative efficacy of the models in predicting fluid viscosity. Both models were used in conjunction with fixed bond lengths and bond angles, but different torsional potentials were investigated. The commonly used Ryckaert—Bellemans intermolecular potential model, which accurately predicts viscosities for short straight-chain alkanes, produced values for branched and long-chain alkanes that were significantly below experimental values. Likewise, a more complex UA model that uses transferrable site potentials and is commonly used to simulate thermodynamic properties also under predicted viscosities for branched and long-chain molecules. The UA models were also found to be density dependent, substantially under predicting viscosity at high liquid densities for all model fluids tested. Predicted viscosities using AA intermolecular potential models were generally substantially too large compared to experiment when using model parameters from the literature, even though thermodynamic properties were adequately predicted. However, evidence suggests that accurately modeling the hydrogen interactions and the rotation potential of methyl groups is essential for accurate viscosity simulations. Therefore, a new set of parameters for the hydrogen interactions was regressed using viscosity simulations of 2-methylpropane and n-pentane. Like the UA model, the AA model with the new parameters is still somewhat density dependent, but gives reasonably accurate predictions of viscosity for most fluids.

Original Publication Citation

Allen, William and Richard L. Rowley. "Predicting the viscosity of alkanes using nonequilibrium molecular dynamics: Evaluation of intermolecular potential models." The Journal of Chemical Physics 16 (1997): 1273-1281

Document Type

Peer-Reviewed Article

Publication Date

1997-06-22

Permanent URL

http://hdl.lib.byu.edu/1877/1459

Publisher

AIP

Language

English

College

Ira A. Fulton College of Engineering and Technology

Department

Chemical Engineering

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