paper

Unraveling the glass-like dynamic heterogeneity in ring polymer melts: From semi-flexible to stiff chain

arXiv:2305.15711 · doi:10.1021/acspolymersau.3c00013

Abstract

Ring polymers are an intriguing class of polymers with unique physical properties, and understanding their behavior is important for developing accurate theoretical models. In this study, we investigate the effect of chain stiffness and monomer density on static and dynamic behaviors of ring polymer melts using molecular dynamics simulations. Our first focus is on the non-Gaussian parameter of center of mass displacement as a measure of dynamic heterogeneity, which is commonly observed in glass-forming liquids. We find that the non-Gaussianity in the displacement distribution increases with the monomer density and stiffness of the polymer chains, suggesting that excluded volume interactions between centers of mass have a stronger effect on the dynamics of ring polymers. We then analyze the relationship between the radius of gyration and monomer density for semi-flexible and stiff ring polymers. Our results indicate that the relationship between the two varies with chain stiffness, which can be attributed to the competition between repulsive forces inside the ring and from adjacent rings. Finally, we study the dynamics of bond-breakage virtually connected between the centers of mass of rings to analyze the exchanges of inter-molecular networks of bonds. Our results demonstrate that the dynamic heterogeneity of bond-breakage is coupled with the non-Gaussianity in ring polymer melts, highlighting the importance of bond-breaking method in determining the inter-molecular dynamics of ring polymer melts. Overall, our study provides insights into the fundamental mechanism of ring polymers and sheds light on the factors that govern their dynamic behavior.

arXiv comment11 pages, 7 figures, to appear in ACS Polymers Au

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