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Dynamically consistent coarse-grain simulation model of chemically specific polymer melts via friction parameterization

Published

Author(s)

Lilian C. Johnson, Frederick R. Phelan Jr.

Abstract

Coarse-grained (CG) models of polymers involve grouping many atoms in an all-atom (AA) representation into single sites to reduce computational effort yet retain the hierarchy of length and time scales inherent to macromolecules. Parameterization of such models is often via "bottom-up" methods, which preserve chemical-specificity, but suffer from artificially accelerated dynamics with respect to the AA model from which they were derived. Here, we study the combination of a bottom-up CG model with a dissipative potential as a means to obtain a chemically specific and dynamically correct model. We generate the conservative part of the force-field using the iterative Boltzmann inversion (IBI) method which seeks to recover the AA structure. This is augmented with the dissipative Langevin thermostat which introduces a single parameterizable friction factor to correct the unphysically fast dynamics of the IBI-generated force-field. We study this approach for linear polystyrene oligomer melts for three separate systems with 11, 21, and 41 monomers per chain and a mapping of one monomer per CG site. To parameterize the friction factor, target values are extracted from the AA dynamics using translational monomer diffusion, translational chain diffusion, and rotational chain motion to test the consistency of the parameterization across different modes of motion. We find that the value of friction parameter needed to bring the CG dynamics in line with AA target values varies based on the mode of parametrization with short-time monomer translational dynamics requiring the highest values, long-time chain translational dynamics requiring the lowest values, and rotational dynamics falling in between. The friction ranges most widely for the shortest chains and the span narrows with increasing chain length. For longer chains, a practical working value of the friction parameter may be derived from the rotational dynamics, owing to the contribution of multiple relaxation modes to chain rotation and a lack of sensitivity of the translational dynamics at these intermediate levels of friction. A study of equilibrium chain structure reveals that all chains studied are non-Gaussian. However, longer chains better approximate ideal chain dimensions than more rod-like shorter chains and thus are most closely described by a single friction parameter. We also find that the separability of the conservative and dissipative potentials is preserved.
Citation
The Journal of Chemical Physics
Volume
154
Issue
8

Keywords

molecular dynamics, coarse-grained modeling, polymer dynamics, polystyrene, iterative Boltzmann inversion, Langevin dynamics

Citation

Johnson, L. and Phelan, F. (2021), Dynamically consistent coarse-grain simulation model of chemically specific polymer melts via friction parameterization, The Journal of Chemical Physics, [online], https://doi.org/10.1063/5.0034910, https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=931227 (Accessed August 19, 2022)
Created February 24, 2021, Updated July 28, 2021