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Arm retraction dynamics of entangled star polymers: a forward-flux sampling method study

Zhu, J., Likhtman, A. E. and Wang, Z. (2017) Arm retraction dynamics of entangled star polymers: a forward-flux sampling method study. The Journal of Chemical Physics, 147 (4). 044907. ISSN 0021-9606

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To link to this item DOI: 10.1063/1.4995422

Abstract/Summary

The study of dynamics and rheology of well-entangled branched polymers remains a challenge for computer simulations due to the exponentially growing terminal relaxation times of these polymers with increasing molecular weights. We present an efficient simulation algorithm for studying the arm retraction dynamics of entangled star polymers by combining the coarse-grained slip-spring (SS) model with the forward-flux sampling (FFS) method. This algorithm is first applied to simulate symmetric star polymers in the absence of constraint release (CR). The reaction coordinate for the FFS method is determined by finding good agreement of the simulation results on the terminal relaxation times of mildly entangled stars with those obtained from direct shooting SS model simulations with the relative difference between them less than $5\%$. The FFS simulations are then carried out for strongly entangled stars with arm lengths up to $16$ entanglements that are far beyond the accessibility of brute force simulations in the non-CR condition. Apart from the terminal relaxation times, the same method can also be applied to generate the relaxation spectra of all entanglements along the arms which are desired for the development of quantitative theories of entangled branched polymers. Furthermore, we propose a numerical route to construct the experimentally measurable relaxation correlation functions by effectively linking the data stored at each interface during the FFS runs. The obtained star arm end-to-end vector relaxation functions $\Phi(t)$ and the stress relaxation function $G(t)$ are found to be in reasonably good agreement with standard SS simulation results in the terminal regime. Finally, we demonstrate that this simulation method can be conveniently extended to study arm-retraction problem in entangled star polymer melts with CR by modifying the definition of the reaction coordinate.

Item Type:Article
Refereed:Yes
Divisions:Faculty of Science > School of Mathematical, Physical and Computational Sciences > Department of Mathematics and Statistics
ID Code:71476
Publisher:American Institute of Physics

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