Comparison of Friction Parametrization from Dynamics and Material Properties for a Coarse-Grained Polymer Melt

Published

July 31, 2023

Author(s)

Lilian Johnson, Frederick R. Phelan Jr.

Abstract

In this work, we extend an approach to coarse-grained (CG) modeling for polymer melts in which the conservative potential is parametrized using the iterative Boltzmann inversion (IBI) method and the accelerated dynamics inherent to IBI are corrected using the dissipative Langevin thermostat with a single tunable friction parameter (J. Chem. Phys. 2021, 154, 084114). Diffusive measures from picoseconds to nanoseconds are used to determine the Langevin friction factor to apply to the CG model to recover all-atom (AA) dynamics; the resulting friction factors are then compared for consistency. Here, we additionally parametrize the CG dynamics using a material property, the zero-shear viscosity, which we measure using the Green−Kubo (GK) method. Two materials are studied, squalane as a function of temperature and the same polystyrene oligomers previously studied as a function of chain length. For squalane, the friction derived from the long-time diffusive measures and the viscosity all strongly increase with decreasing temperature, showing an Arrhenius-like dependence, and remain consistent with each other over the entire temperature range. In contrast, the friction required for the picosecond diffusive measurement, the Debye−Waller factor, is somewhat lower than the friction from long-time measures and relatively insensitive to temperature. A time-dependent friction would be required to exactly reproduce the AA measurements during the caging transition connecting these two extremes over the entire timespan at this level of coarse-graining. For the polystyrene oligomers for which we previously characterized the diffusive friction, the viscosity-parametrized frictions are consistent with the diffusive measures for the smallest chain length. However, for the longer chains, we find different trends based on measurement method with friction derived from rotational diffusion remaining nearly constant, friction derived from translational diffusion showing a modestly increasing trend, and viscosity-derived friction showing a modest decreasing trend. This seems to indicate that there is some sensitivity of the friction measurement method for systems with increased relaxation times and that in particular, the unsteady dynamics of the individual parametrization schemes plays a role in this. Increased difficulty in applying the GK method with increasing relaxation time of the longer chain systems is also discussed. Overall, we find that when the material is in a high-temperature melt state and the viscosity measurement is reliable, the friction parametrization from the diffusive friction measures is consistent and the lower cost diffusive parametrization is a reliable means for modeling viscosity. Our data give insight into the time-dependent friction one might compute using a non-Markovian approach to enable the recovery of AA dynamics over a wider range of time scales than can be computed using a single friction.

Citation

Journal of Physical Chemistry B

Volume

127

Issue

31

Pub Type

Journals

Download Paper

https://doi.org/10.1021/acs.jpcb.3c03273

Local Download

Keywords

Molecular Dynamics (MD), Coarse-Graining, Coarse-Grained Force-Field, Iterative Boltzmann Inversion, Langevin Friction Factor, Mean-Squared Displacement, Debye-Waller Factor, Green-Kubo Viscosity, Squalane, Polystyrene, Polymer Melts, Polymer Dynamics

Citation

Johnson, L. and Phelan Jr., F. (2023), Comparison of Friction Parametrization from Dynamics and Material Properties for a Coarse-Grained Polymer Melt, Journal of Physical Chemistry B, [online], https://doi.org/10.1021/acs.jpcb.3c03273, https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=935567 (Accessed April 27, 2024)