Numerical calculation of free-energy barriers for entangled polymer nucleation.
The Journal of chemical physics
American Institute of Physics
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Tang, X., Tian, F., Xu, T., Li, L., & Reinhardt, A. (2020). Numerical calculation of free-energy barriers for entangled polymer nucleation.. The Journal of chemical physics, 152 (22), 224904. https://doi.org/10.1063/5.0009716
The crystallisation of entangled polymers from their melt is investigated using computer simulation with a coarse-grained model. Using hybrid Monte Carlo simulations enables us to probe the behaviour of long polymer chains. We identify solid-like beads with a centrosymmetry local order parameter and compute the nucleation free-energy barrier at relatively high supercooling with adaptive-bias windowed umbrella sampling. Our results demonstrate that the critical nucleus sizes and the heights of free-energy barriers do not significantly depend on the molecular weight of the polymer; however, the nucleation rate decreases with increasing molecular weight. Moreover, an analysis of the composition of the critical nucleus suggests that intra-molecular growth of the nucleated cluster does not contribute significantly to crystallisation for this system.
Is supplemented by: https://doi.org/10.17863/CAM.51140
National Key R&D Program of China (2016YFB0302500); National Natural Science Foundation of China (51633009); Royal Society Newton Mobility Grant (MBAG/240 RG82754)
External DOI: https://doi.org/10.1063/5.0009716
This record's URL: https://www.repository.cam.ac.uk/handle/1810/305615
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