Martelli Fausto, Leoni Fabio, Sciortino Francesco, Russo John
IBM Research Europe, Hartree Centre, Daresbury WA4 4AD, United Kingdom.
School of Mathematics, University of Bristol, Bristol BS8 1UG, United Kingdom.
J Chem Phys. 2020 Sep 14;153(10):104503. doi: 10.1063/5.0018923.
The origin of water anomalies hides in an experimentally inaccessible region of the phase diagram known as no-man's land, bounded at low temperature by the domain of stability of amorphous glasses, and at high temperature by the homogeneous nucleation line, below which liquid water loses its metastability. The existence of at least two different forms of glass on one side, i.e., the low-density amorphous (LDA) and the high-density amorphous (HDA) ices, and of one anomalous liquid on the other side, points to a hidden connection between these states, whose understanding has the potential to uncover what happens in no-man's land and shed light on the complex nature of water's behavior. Here, we develop a Neural Network scheme capable of discerning local structures beyond tetrahedrality. Applied over a wide region of the water's phase diagram, we show that the local structures that characterize both LDA and HDA amorphous phases are indeed embedded in the supercooled liquid phase. Remarkably, the rapid increase in the LDA-like population with supercooling occurs in the same temperature and pressure region where thermodynamic fluctuations are maximized, linking these structures with water's anomalies. At the same time, the population of HDA-like environments rapidly increases with pressure, becoming the majority component at high density. Our results show that both LDA and HDA are genuine glasses, and provide a microscopic connection between the non-equilibrium and equilibrium phase diagrams of water.
水异常现象的起源隐藏在相图中一个实验上无法触及的区域,即所谓的“无人区”,该区域在低温下由非晶态玻璃的稳定域界定,在高温下由均匀成核线界定,低于此线液态水会失去其亚稳性。一侧存在至少两种不同形式的玻璃,即低密度非晶态(LDA)和高密度非晶态(HDA)冰,另一侧存在一种异常液体,这表明这些状态之间存在隐藏的联系,对其理解有可能揭示“无人区”中发生的情况,并阐明水行为的复杂本质。在此,我们开发了一种能够识别超越四面体结构的局部结构的神经网络方案。应用于水相图的广泛区域,我们表明表征LDA和HDA非晶相的局部结构确实嵌入在过冷液相中。值得注意的是,随着过冷,类似LDA的粒子数迅速增加发生在热力学涨落最大化的相同温度和压力区域,将这些结构与水的异常现象联系起来。同时,类似HDA环境的粒子数随压力迅速增加,在高密度时成为主要成分。我们的结果表明LDA和HDA都是真正的玻璃,并提供了水的非平衡相图和平衡相图之间的微观联系。