Analysis of Slow Modes in Ring Polymers: Threading of Rings Controls Long-Time Relaxation

Atomistic configurations of pure, precisely monodisperse ring poly­(ethylene oxide) (PEO) melts accumulated in the course of very long molecular dynamics (MD) simulations at T = 413 K and P = 1 atm have been subjected to a detailed geometric analysis involving three steps (reduction to ensembles of coarse-grained paths, triangulation of the resulting three-dimensional polygons, and analysis of interpenetrations using vector calculus) in order to locate ring–ring threading events and quantify their strength and survival times. A variety of threading situations have been identified corresponding to single and multiple penetrations. The percentage of inter-ring threadings that correspond to full penetrations has also been quantified. By repeating the analysis for several PEO melts, the dependence of the degree of inter-ring threading on molecular weight (MW) has been obtained. Simulations with MWs up to 10 times the reported entanglement molecular weight (M e) of linear PEO have revealed several multiple threading events in all systems, with their relative number increasing with increasing MW. Our analysis indicates the existence of strong ring–ring topological interactions, which can last up to several times the corresponding average orientational ring polymer relaxation time. We show that these ring–ring interactions, together with the additional ring–linear threadings due to the remaining linear impurities, can explain the appearance of slow relaxation modes observed experimentally in entangled rings.