Molecular shape transitions driven by an external force: the case of polymer chains with transient knotted loops
Literature Information
We study the simulated relaxation behaviour of grafted polyethylene with transient topological constraints. We employ a “soft” steered molecular dynamics algorithm, whereby chain stress is introduced by a sequence of stretchings/compressions at the free (nongrafted) end of the chain. Each bond perturbation is allowed to dissipate within the chain using constrained molecular dynamics, before the next perturbation is applied. Using a knotted-loop as a model for transient entanglement, we show the occurrence of a range of shape transitions that are not visible in the mean molecular size. During the stretching phase, the formation of rigid and tight knotted loops can be recognized by the variation in entanglement complexity or the local compactness. We show that the stress due to stretching can be removed reversibly during the compression phase, eliciting the delocalization of even very tight knots. We also find that a tight knot is still marginally diffusive along the chain whenever the external stretching couples to chain torsions.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










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