Molecular Dynamics Simulation of Pure n-Alkanes and Their Mixtures at Elevated Temperatures Using Atomistic and Coarse-Grained Force Fields.

Research paper by Konstantinos D KD Papavasileiou, Loukas D LD Peristeras, Andreas A Bick, Ioannis George IG Economou

Indexed on: 17 Apr '20Published on: 30 Jun '19Published in: Journal of Physical Chemistry B


The properties of higher n-alkanes and their mixtures is a topic of significant interest for the oil and chemical industry. However, the experimental data at high temperatures are scarce. The present study focuses on simulating n-dodecane, n-octacosane, their binary mixture at a n-dodecane mole fraction of 0.3, and a model mixture of the commercially available hydrocarbon wax SX-70 to evaluate the performance of several force fields on the reproduction of properties such as liquid densities, surface tension and viscosities. Molecular Dynamics (MD) simulations over a broad temperature range from 323.15 to 573.15 K were employed in examining a broad set of atomistic molecular models assessed for the reproduction of experimental data. The well-established united atom TraPPE (TraPPE-UA) was compared against the optimized version of OPLS for long n-alkanes, L-OPLS, as well as Lipid14 and MARTINI force fields. All models qualitatively reproduce the temperature dependence of the aforementioned properties, but TraPPE-UA was found to reproduce liquid densities most accurately and consistently over the entire temperature range. TraPPE-UA and MARTINI were very successful in reproducing surface tensions and L-OPLS was found to be the most accurate in reproducing the measured viscosities as compared to the other models. Our simulations show that these widely used force fields originating from the world of biomolecular simulations, are suitable candidates in the study of n-alkane properties, both in the pure and mixture states.