Estimation of Solvent Diffusion Coefficients Using Molecular Dynamics Simulations

Abstract

Molecular dynamics simulations have been used to investigate diffusion in two commonly used industrial solvents, toluene and tetrahydrofuran. Several different models for the solvents are compared (flexible vs. rigid, all-atom vs. united atom), and it is found that united atom and all-atom models of the solvents produce very different diffusion coefficients at the experimental density. This disagreement can be explained by the pressure dependence of the diffusion coefficient, which is found to vary in accord with the Chapman-Enskog result for hard spheres. It is recommended that force fields be parametrized carefully to produce reasonable pressures at the experimental densities, or that simulations be carried out at constant pressure, if they are to be used for the purposes of calculating transport coefficients.