论文标题
通过在等异构体合奏中探测的两个模型玻璃形成液体中拉伸指数松弛的显微镜起源
The microscopic origins of stretched exponential relaxation in two model glass-forming liquids as probed by simulations in the isoconfigurational ensemble
论文作者
论文摘要
超冷玻璃形成液体中拉伸指数松弛的起源是有关这些流体异常动力学的中心问题之一。长期以来,对这种现象的主要解释是,空间平均在局部指数弛豫过程的异质分布上平均会导致拉伸。在这里,我们对等型集合中的模型聚合物和小分子玻璃形成剂进行了模拟,以表明伸展运动是由空间平均和局部非局部放松的组合而出现的。结果表明,表现出比平均水平快的液体中的位置倾向于在局部伸展的松弛表现出来,而较慢的放松域则表现出压缩的指数弛豫。我们表明,通过Debye-Waller因子测量的局部笼子可以预测局部拉伸,反之亦然。这种现象学在局部平衡玻璃的局部松弛中与平衡的低密度和过度密集的玻璃的动力学相似,这同样在其拉伸程度与压缩程度上表现出不对称性。根据这些结果,我们假设平衡玻璃形成液体中的局部拉伸和压缩是由于在单个局部松弛时间内的粒子迁移率的演变而导致的,而较慢的颗粒趋向于加速,反之亦然。除了提供有关拉伸松弛的起源的新见解外,这些结果还对通过介电光谱等计量学测量的拉伸指数的解释具有影响:测量的拉伸指数不能普遍解释为对潜在松弛时间的宽度的直接衡量。
The origin of stretched exponential relaxation in supercooled glass-forming liquids is one of the central questions regarding the anomalous dynamics of these fluids. The dominant explanation for this phenomenon has long been the proposition that spatial averaging over a heterogeneous distribution of locally exponential relaxation processes leads to stretching. Here we perform simulations of model polymeric and small-molecule glass-formers in the isoconfigurational ensemble to show that stretching instead emerges from a combination of spatial averaging and locally nonexponential relaxation. Results indicate that localities in the fluid exhibiting faster-than-average relaxation tend to exhibit locally stretched relaxation, whereas slower-than-average relaxing domains exhibit compressed exponential relaxation. We show that local stretching is predicted by loose local caging, as measured by the Debye-Waller factor, and vice versa. This phenomenology in the local relaxation of in-equilibrium glasses parallels the dynamics of out of equilibrium under-dense and over-dense glasses, which likewise exhibit an asymmetry in their degree of stretching vs compression. On the basis of these results, we hypothesize that local stretching and compression in equilibrium glass-forming liquids results from evolution of particle mobilities over a single local relaxation time, with slower particles tending towards acceleration and vice versa. In addition to providing new insight into the origins of stretched relaxation, these results have implications for the interpretation of stretching exponents as measured via metrologies such as dielectric spectroscopy: measured stretching exponents cannot universally be interpreted as a direct measure of the breadth of an underlying distribution of relaxation times.