Self-diffusion and shear viscosity of pure 1-alkanol unary system: molecular dynamics simulation and review of experimental data

Abstract

Self-diffusion coefficients and shear viscosity coefficients of pure 1-alkanol liquids from methanol to 1-hexanol were predicted using molecular dynamics (MD) simulations. These coefficients have been calculated using the Green–Kubo and Einstein methods at a range of temperatures of 200–330 K with increments of 10 K. Two force fields, TraPPE-UA and OPLS-AA were applied. The predicted results were compared to the experimental data, and the activation energies for self-diffusion and shear viscosity were calculated using the Arrhenius equation. The Stokes–Einstein equation was used to examine its capability in predicting the relationship between self-diffusion and shear viscosity, and the effective hydrodynamic radius was determined using both the experimental data and the results from MD simulations. The TraPPE-UA force field showed better results for the transport properties of methanol, while the OPLS-AA force field performed well for predicting shear viscosity but weakly for self-diffusion, particularly at low temperatures and for 1-alkanol with higher methylene numbers. Using the mean squared displacement method for self-diffusion was found to be more accurate than the Green–Kubo method, while the Green–Kubo method was slightly better for calculating shear viscosity. The Stokes–Einstein equation is valid for pure 1-alkanol liquids with temperature-dependent effective hydrodynamic radius.