Bristol Centre for Complexity Sciences, University of Bristol, Bristol BS8 1TS, United Kingdom.
J Chem Phys. 2013 Mar 28;138(12):12A535. doi: 10.1063/1.4790515.
We study the relationship between local structural ordering and dynamical heterogeneities in a model glass-forming liquid, the Wahnström mixture. A novel cluster-based approach is used to detect local energy minimum polyhedral clusters and local crystalline environments. A structure-specific time correlation function is then devised to determine their temporal stability. For our system, the lifetime correlation function for icosahedral clusters decays far slower than for those of similarly sized but topologically distinct clusters. Upon cooling, the icosahedra form domains of increasing size and their lifetime increases with the size of the domains. Furthermore, these long-lived domains lower the mobility of neighboring particles. These structured domains show correlations with the slow regions of the dynamical heterogeneities that form on cooling towards the glass transition. Although icosahedral clusters with a particular composition and arrangement of large and small particles are structural elements of the crystal, we find that most icosahedral clusters lack such order in composition and arrangement and thus local crystalline ordering makes only a limited contribution to this process. Finally, we characterize the spatial correlation of the domains of icosahedra by two structural correlation lengths and compare them with the four-point dynamic correlation length. All the length scales increase upon cooling, but in different ways.
我们研究了模型玻璃形成液体——Wahnström 混合物中局部结构有序性和动力学非均匀性之间的关系。采用了一种新的基于团簇的方法来检测局部能量最小多面体团簇和局部晶态环境。然后设计了一种结构特异性的时相关函数来确定它们的时间稳定性。对于我们的系统,二十面体团簇的寿命相关函数的衰减速度远慢于具有相似大小但拓扑不同的团簇。冷却时,二十面体形成越来越大的尺寸域,其寿命随域尺寸的增加而增加。此外,这些长寿命的域降低了相邻粒子的迁移率。这些结构化的域与在冷却到玻璃转变过程中形成的动力学非均匀性的缓慢区域相关。尽管具有特定组成和大、小粒子排列的二十面体团簇是晶体的结构元素,但我们发现大多数二十面体团簇在组成和排列上缺乏这种有序性,因此局部晶体有序性对此过程的贡献有限。最后,我们通过两个结构相关长度来描述二十面体团簇域的空间相关性,并将其与四点动态相关长度进行比较。所有长度尺度都随着冷却而增加,但方式不同。