JST-CREST, Institute for Chemical Research, Kyoto University, Gokasho, Uji 611-0011, Japan.
J Chem Phys. 2012 Sep 21;137(11):114903. doi: 10.1063/1.4752768.
In entangled polymer systems, there are several characteristic time scales, such as the entanglement time and the disengagement time. In molecular simulations, the longest relaxation time (the disengagement time) can be determined by the mean square displacement (MSD) of a segment or by the shear relaxation modulus. Here, we propose the relative fluctuation analysis method, which is originally developed for characterizing large fluctuations, to determine the longest relaxation time from the center of mass trajectories of polymer chains (the time-averaged MSDs). Applying the method to simulation data of entangled polymers (by the slip-spring model and the simple reptation model), we provide a clear evidence that the longest relaxation time is estimated as the crossover time in the relative fluctuations.
在缠结聚合物体系中,存在几个特征时间尺度,例如缠结时间和解缠时间。在分子模拟中,最长的弛豫时间(解缠时间)可以通过片段的均方位移(MSD)或剪切松弛模量来确定。在这里,我们提出相对波动分析方法,该方法最初是为了表征大波动而开发的,可通过聚合物链质心轨迹(时间平均 MSD)确定最长弛豫时间。将该方法应用于缠结聚合物的模拟数据(通过滑链-弹簧模型和简单蠕动模型),我们提供了明确的证据,表明最长弛豫时间可作为相对波动中的交叉时间来估计。