Enhancing NEMD with automatic shear rate sampling to model viscosity and correction of systematic errors in modeling density: Application to linear and light branched alkanes.

We perform molecular dynamics simulations to model density as a function of temperature for 74 alkanes with 5–10 carbon atoms and non-equilibrium molecular dynamics simulations in the NVT ensemble to model the kinematic viscosity of 10 linear alkanes as a function of molecular weight, pressure, and temperature. To model density, we perform simulations in the NPT ensemble before applying correction factors to exploit the systematic error in the SciPCFF force field and compare the results to experimental values, obtaining an average absolute deviation of 3.4 g l at 25 °C and of 7.2 g l at 100 °C. We develop a sampling algorithm that automatically selects good shear rates at which to perform viscosity simulations in the NVT ensemble and use the Carreau model with weighted least squares regression to extrapolate Newtonian viscosity. Viscosity simulations are performed at experimental densities and show an excellent agreement with experimental viscosities, with an average percent deviation of −1% and an average absolute percent deviation of 5%. Future plans to study and apply the sampling algorithm are outlined. [ABSTRACT FROM AUTHOR]