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Flory-type theory of a knotted ring polymer

机译:打结环聚合物的弗洛里型理论

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摘要

A mean field theory of the effect of knots on the statistical mechanics of ring polymers is presented. We introduce a topological invariant which is related to the primitive path in the ''polymer in the lattice of obstacles'' model and use it to estimate the entropic contribution to the free energy of a nonphantom ring polymer. The theory predicts that the volume of the maximally knotted ring polymer is independent of solvent quality and that the presence of knots suppresses both the swelling of the ring in a good solvent and its collapse in a poor solvent. The probability distribution of the degree of knotting is estimated and it is shown that the most probable degree of knotting upon random closure of the chain grows dramatically with chain compression. The theory also predicts some unexpected phenomena such as ''knot segregation'' in a swollen polymer ring, when the bulk of the ring expels all the entanglements and swells freely, with all the knots concentrated in a relatively small and compact part of the polymer.
机译:提出了一种平均节理论的结对环聚合物的统计力学的影响。我们引入了与“障碍晶格中的聚合物”模型中的原始路径有关的拓扑不变量,并使用它来估计熵对非幻影环聚合物的自由能的贡献。该理论预测最大打结的环聚合物的体积与溶剂质量无关,并且结的存在既抑制了环在良溶剂中的溶胀,又抑制了在不良溶剂中的塌陷。估计了打结程度的概率分布,结果表明,随机压缩链时最可能打结的程度随着链条压缩而急剧增加。该理论还预测了一些出乎意料的现象,例如溶胀的聚合物环中的“结偏析”,当该环的大部分排出所有缠结并自由膨胀时,所有结都集中在聚合物的一个相对较小且紧凑的部分中。

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