Faculty of Science, University of Split, Rudjera Boškovića 33, 21000 Split, Croatia.
Laboratoire de Physique Théorique de la Matiére Condensée (UMR CNRS 7600), Sorbonne Université, 4 Place Jussieu, Paris CEDEX 05 F75252, France.
J Phys Chem B. 2023 Jun 29;127(25):5645-5654. doi: 10.1021/acs.jpcb.3c01077. Epub 2023 Jun 19.
Liquids are archetypes of disordered systems, yet liquids of polar molecules are locally more ordered than nonpolar molecules, due to the Coulomb interaction based charge ordering phenomenon. Hydrogen bonded liquids, such as water or alcohols, for example, represent a special type of polar liquids, in that they form labile clustered local structures. For water, in particular, hydrogen bonding and the related local tetrahedrality, play an important role in the various attempts to understand this liquid. However, labile structures imply dynamics, and it is not clear how it affects the understanding of this type of liquids from purely static point of view. Herein, we propose to reconsider hydrogen bonding as a charge ordering process. This concept allows us to demonstrate the insufficiency of the analysis of the microscopic structure based solely on static pair correlation functions, and the need for dynamical correlation functions, both in real and reciprocal space. The subsequent analysis allows to recover several aspects of our understanding of hydrogen bonded liquids, but from the charge order perspective. For water, it confirms the jump rotation picture found recently, and it allows to rationalize the contradicting pictures that arise when following the interpretations based on hydrogen bonding. For alcohols, it allows to understand the dynamical origin of the scattering prepeak, which does not exist for water, despite the fact that both these liquids have very similar hydroxyl group chain clusters. The concept of charge ordering complemented by the analysis of dynamical correlation functions appear as a promising way to understand microheterogeneity in complex liquids and mixtures from kinetics point of view.
液体是无序系统的原型，但由于基于库仑相互作用的电荷有序现象，极性分子的液体在局部上比非极性分子更有序。氢键液体，如水或醇类，代表了一种特殊类型的极性液体，因为它们形成不稳定的聚集局部结构。特别是对于水，氢键和相关的局部四面体结构在试图理解这种液体的各种尝试中起着重要作用。然而，不稳定的结构意味着动力学，并且不清楚它如何从纯静态角度影响对这类液体的理解。在此，我们建议重新将氢键视为电荷有序过程。这个概念使我们能够证明仅基于静态对关联函数分析微观结构的不充分性，以及在实空间和倒易空间中都需要动态相关函数。随后的分析允许我们从电荷有序的角度重新审视对氢键液体的理解的几个方面。对于水，它证实了最近发现的跳跃旋转图像，并允许合理化基于氢键的解释所产生的相互矛盾的图像。对于醇类，它允许理解散射前峰的动力学起源，尽管这两种液体都具有非常相似的羟基链簇，但水却不存在这种前峰。电荷有序的概念加上对动态相关函数的分析，似乎是从动力学角度理解复杂液体和混合物的微观不均匀性的一种很有前途的方法。
