Improvements and limitations of Mie λ-6 potential for prediction of saturated and compressed liquid viscosity.

Abstract Over the past decade, the Mie λ-6 (generalized Lennard-Jones) potential has grown in popularity due to its improved accuracy for predicting vapor-liquid coexistence densities and pressure compared to the traditional Lennard-Jones 12-6 potential. This manuscript explores the hypothesis that greater accuracy in characterizing the coexistence properties may lead to greater accuracy for viscosity predictions. Four united-atom force fields are considered in detail: the Transferable Potentials for Phase Equilibria (TraPPE-UA and the recently developed TraPPE-2) model of Siepmann and coworkers, the Transferable Anisotropic Mie (TAMie) model of Gross and coworkers, the fourth generation anisotropic-united-atom (AUA4) model of Ungerer and coworkers, and the model of Potoff and coworkers. Equilibrium molecular dynamics simulations are analyzed using the Green-Kubo method for viscosity characterization. Simulations are performed for linear alkanes with two to twenty-two carbons and branched alkanes with four to eight carbons. Simulation conditions follow the saturated liquid from reduced temperatures of 0.5–0.85 and along the 293 K isotherm in the dense liquid region. In general, the more accurate force fields for coexistence properties do indeed predict viscosity more accurately. For saturated liquids, both Mie-based potential models (Potoff and TAMie) provide roughly 10% accuracy for linear alkanes, while deviations are between 20 and 50% for TraPPE-UA. For branched alkanes, the performance is slightly diminished, but Potoff still provides roughly 15–20% accuracy, while the TAMie force field results in deviations of 20–40%, and TraPPE-UA has deviations of approximately 25–60%. The AUA4 deviations are 10–20% for ethane and 30–60% for 2,2-dimethylpropane, the only compounds tested with the AUA4 force field. The TraPPE-2 deviations for ethane are similar to those using the original TraPPE force field, namely, between 10 and 20%. The percent deviations for each compound and force field tend to increase with decreasing temperature, with the exception of the Potoff deviations for propane, which are nearly constant to the triple point temperature. For compressed liquids, the Mie-based potential models perform better once again than the Lennard-Jones-based force fields, but tend to over estimate the viscosity at very high densities. As the Potoff and TAMie models also tend to over estimate the pressure at high densities, a fortuitous cancellation of errors leads to predictions of viscosity with respect to pressure that are accurate to within about 10%. The comparison with experimental viscosity data is limited to pressures below 200 MPa for most normal and branched alkanes. However, accurate predictions are obtained for propane near 1000 MPa with the Potoff force field. [ABSTRACT FROM AUTHOR]