Contributions of force field interaction forms to Green-Kubo viscosity integral in n-alkane case

N Kondratyuk, JOURNAL OF CHEMICAL PHYSICS, 151, 074502 (2019).

DOI: 10.1063/1.5103265

Decades of molecular simulation history proved that the Green-Kubo method for shear viscosity converges without any problems in atomic and simple molecular liquids, unlike liquids with high values of viscosity. In the case of highly viscous liquids, the time decomposition method was developed in 2015 by Maginn and co-authors Y. Zhang, A. Otani, and E. J. Maginn, J. Chem. Theory Comput. 11, 3537-3546 (2015) which allows us to improve the convergence of the Green-Kubo integral. In this paper, the contributions of intramolecular and intermolecular force field parts to the viscosity integral are discovered to gain the understanding of the Green-Kubo method. The n-alkanes from n-ethane to n-pentane at 330 K in the optimized potentials for liquid simulations-all atom force field are used as reference models. The dependencies of these contributions and decay times of the corresponding correlation functions on the chain length are observed. The nonequilibrium simulations are carried out to verify the Green-Kubo results. The obtained values of viscosity are compared with experimental data.

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