A central paradigm of polymer physics states that chains in melts behave like random walks as intra- and interchain interactions effectively cancel each other out. Likewise, θ-chains, i.e., chains at the transition from a swollen coil to a globular phase, are also thought to behave like ideal chains, as attractive forces are counterbalanced by repulsive entropic contributions. While the simple mapping to an equivalent Kuhn chain works rather well in most scenarios with corrections to scaling, random walks do not accurately capture the topology and knots, particularly for flexible chains. In this paper, we demonstrate with Monte Carlo and molecular dynamics simulations that chains in polymer melts and θ-chains not only agree on a structural level for a range of stiffnesses but also topologically. They exhibit similar knotting probabilities and knot sizes, both of which are not captured by ideal chain representations. This discrepancy comes from the suppression of small knots in real chains, which is strongest for very flexible chains because excluded volume effects are still active locally and become weaker with increasing semiflexibility. Our findings suggest that corrections to ideal behavior are indeed similar for the two scenarios of real chains and that the structure and topology of a chain in a melt can be approximately reproduced by a corresponding θ-chain.
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14 October 2024
Research Article|
October 10 2024
Topological comparison of flexible and semiflexible chains in polymer melts with θ-chains
Special Collection:
Monte Carlo methods, 70 years after Metropolis et al. (1953)
Maurice P. Schmitt
;
Maurice P. Schmitt
(Data curation, Formal analysis, Investigation, Methodology, Software, Visualization, Writing – original draft, Writing – review & editing)
1
Institut für Physik, Johannes Gutenberg-Universität Mainz
, Staudinger Weg 9, 55099 Mainz, Germany
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Sarah Wettermann
;
Sarah Wettermann
(Data curation, Formal analysis, Investigation, Methodology, Software, Writing – original draft, Writing – review & editing)
1
Institut für Physik, Johannes Gutenberg-Universität Mainz
, Staudinger Weg 9, 55099 Mainz, Germany
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Kostas Ch. Daoulas
;
Kostas Ch. Daoulas
a)
(Conceptualization, Data curation, Formal analysis, Project administration, Software, Supervision, Validation, Writing – original draft, Writing – review & editing)
2
Max Planck Institute for Polymer Research
, Ackermannweg 10, 55128 Mainz, Germany
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Hendrik Meyer
;
Hendrik Meyer
b)
(Conceptualization, Data curation, Formal analysis, Investigation, Methodology, Project administration, Resources, Software, Supervision, Validation, Writing – original draft, Writing – review & editing)
3
Institut Charles Sadron, Université de Strasbourg, CNRS UPR 22
, 23 rue du Loess-BP 84047, 67034 Strasbourg, France
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Peter Virnau
Peter Virnau
c)
(Conceptualization, Project administration, Resources, Supervision, Validation, Writing – original draft, Writing – review & editing)
1
Institut für Physik, Johannes Gutenberg-Universität Mainz
, Staudinger Weg 9, 55099 Mainz, Germany
c)Author to whom correspondence should be addressed: [email protected]
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c)Author to whom correspondence should be addressed: [email protected]
J. Chem. Phys. 161, 144904 (2024)
Article history
Received:
July 15 2024
Accepted:
September 21 2024
Citation
Maurice P. Schmitt, Sarah Wettermann, Kostas Ch. Daoulas, Hendrik Meyer, Peter Virnau; Topological comparison of flexible and semiflexible chains in polymer melts with θ-chains. J. Chem. Phys. 14 October 2024; 161 (14): 144904. https://doi.org/10.1063/5.0228826
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