Department of Physics, University of Illinois, 1110 West Green Street, Urbana, Illinois 61801, USA.
Phys Rev Lett. 2012 Oct 19;109(16):168306. doi: 10.1103/PhysRevLett.109.168306.
We qualitatively extend a microscopic dynamical theory for the transverse confinement of infinitely thin rigid rods to study topologically entangled melts of flexible polymer chains. Our main result treats coils as ideal random walks of self-consistently determined primitive-path (PP) steps and exactly includes chain uncrossability at the binary collision level. A strongly anharmonic confinement potential ("tube") for a primitive path is derived and favorably compared with simulation results. The relationship of the PP-level theory to two simpler models, the melt as a disconnected fluid of primitive-path steps and a "supercoarse graining" that replaces the entire chain by a needle corresponding to its end-to-end vector, is examined. Remarkable connections between the different levels of coarse graining are established.
我们定性地扩展了一种用于无限细刚性棒的横向约束的微观动力学理论,以研究拓扑纠缠的柔性聚合物链熔体。我们的主要结果将线圈视为自洽确定的原始路径 (PP) 步的理想随机行走,并在二进制碰撞水平上完全包含链不可穿越性。推导了一个强烈非谐的原始路径约束势(“管”),并与模拟结果进行了比较。还研究了 PP 级理论与两个更简单模型之间的关系,即熔体作为原始路径步的不连续流体,以及通过将整个链用对应于其末端到末端向量的针代替的“超粗化”。在不同的粗粒化水平之间建立了显著的联系。