Tanaka Hajime
Research Center for Advanced Science and Technology, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8904, Japan.
Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8505, Japan.
J Phys Chem B. 2025 Jan 23;129(3):789-813. doi: 10.1021/acs.jpcb.4c06392. Epub 2025 Jan 10.
As a liquid is supercooled toward the glass transition point, its dynamics slow significantly, provided that crystallization is avoided. With increased supercooling, the particle dynamics become more spatially heterogeneous, a phenomenon known as dynamic heterogeneity. Since its discovery, this characteristic of metastable supercooled liquids has garnered considerable attention in glass science. However, the precise physical origins of dynamic heterogeneity remain elusive and widely debated. In this perspective, we examine the relationship between dynamic heterogeneity and structural order, based on numerical simulations of fragile liquids with isotropic potentials and strong liquids with directional interactions. We demonstrate that angular ordering, arising from many-body steric interactions, plays a crucial role in the slow dynamics and dynamic cooperativity of fragile liquids. Additionally, we explore how the growth of static order correlates with slower dynamics. In fragile liquids exhibiting super-Arrhenius behavior, the spatial extent of regions with high angular order grows upon cooling, and the sequential propagation of particle rearrangements within these ordered regions increases the activation energy for particle motion. In contrast, strong liquids with spatially constrained local ordering display a distinct "two-state" dynamic characteristic, marked by a transition between two Arrhenius-type behaviors. We argue that dynamic heterogeneity, irrespective of a liquid's fragility, arises from underlying structural order, with its spatial extent determined by static ordering. This perspective aims to deepen our understanding of the interplay between structural and dynamic properties in metastable supercooled liquids.
当一种液体朝着玻璃化转变点过冷时,只要避免结晶,其动力学就会显著减慢。随着过冷度增加,粒子动力学在空间上变得更加不均匀,这种现象被称为动态不均匀性。自发现以来,亚稳态过冷液体的这一特性在玻璃科学领域引起了相当大的关注。然而,动态不均匀性的确切物理起源仍然难以捉摸,且存在广泛争议。从这个角度出发,我们基于具有各向同性势的脆性液体和具有方向性相互作用的强液体的数值模拟,研究了动态不均匀性与结构有序性之间的关系。我们证明,由多体空间相互作用产生的角向有序性在脆性液体的慢动力学和动态协同性中起着关键作用。此外,我们还探讨了静态有序性的增长如何与较慢的动力学相关联。在表现出超阿伦尼乌斯行为的脆性液体中,高角向有序区域的空间范围在冷却时会增大,并且这些有序区域内粒子重排的顺序传播增加了粒子运动的活化能。相比之下,具有空间受限局部有序性的强液体表现出独特的“双态”动态特性,其特征是在两种阿伦尼乌斯型行为之间转变。我们认为,无论液体的脆性如何,动态不均匀性都源于潜在的结构有序性,其空间范围由静态有序性决定。这一观点旨在加深我们对亚稳态过冷液体中结构和动态性质之间相互作用的理解。