Department of Chemistry, Duke University, Durham, NC 27708, USA.
Proc Natl Acad Sci U S A. 2012 Aug 28;109(35):13939-43. doi: 10.1073/pnas.1211825109. Epub 2012 Aug 13.
The glass problem is notoriously hard and controversial. Even at the mean-field level, little is agreed upon regarding why a fluid becomes sluggish while exhibiting but unremarkable structural changes. It is clear, however, that the process involves self-caging, which provides an order parameter for the transition. It is also broadly assumed that this cage should have a gaussian shape in the mean-field limit. Here we show that this ansatz does not hold. By performing simulations as a function of spatial dimension d, we find the cage to keep a nontrivial form. Quantitative mean-field descriptions of the glass transition, such as mode-coupling theory, density functional theory, and replica theory, all miss this crucial element. Although the mean-field random first-order transition scenario of the glass transition is qualitatively supported here and non-mean-field corrections are found to remain small on decreasing d, reconsideration of its implementation is needed for it to result in a coherent description of experimental observations.
玻璃化转变问题一直以来都极具争议性和困难。即使在平均场水平,对于为什么当流体只表现出不显著的结构变化时却变得迟缓,人们也几乎没有达成共识。然而,很明显,这个过程涉及自囚禁,它为转变提供了一个序参量。人们也普遍认为,在平均场极限下,这个牢笼应该具有高斯形状。在这里,我们表明这种假设并不成立。通过执行作为空间维度 d 的函数的模拟,我们发现牢笼保持着非平凡的形状。玻璃化转变的定量平均场描述,如模式耦合理论、密度泛函理论和复制理论,都忽略了这个关键元素。尽管这里定性地支持玻璃化转变的平均场随机一级相变情景,并且发现非平均场修正在降低 d 时仍然很小,但需要重新考虑其实现,以便对实验观察结果进行一致的描述。