Two-state free-volume model for anomalous dynamics in supercooled water macromolecules undergoing liquid–liquid phase transition

IF 2.8 3区化学 Q3 CHEMISTRY, PHYSICAL

Chemical Physics Letters Pub Date : 2024-10-09 DOI:10.1016/j.cplett.2024.141674

Peizhao Li , Haibao Lu , Tengfei Zheng , Yong-Qing Fu

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Abstract

Modelling anomalous dynamics of complex liquid water is a huge challenge due to its various condensed molecular structures and the associated liquid–liquid phase transitions (LLPTs). In this study, we considered, for the first time, the influences of free volume and entropy on LLPTs for both low-density liquid (LDL) and high-density liquid (HDL) waters. Firstly, we proposed a two-state free-volume model and combined with the Adam-Gibbs models to investigate the dynamic equilibria with free diffusion coefficient, viscosity, glass transition temperature and the anomalous dynamics in the two-state water. Free-energy equation was then developed to explore the constitutive relationships of free volume, entropy and anomalously dynamic behaviors. Finally, analytical results of the proposed two-state free-volume model were compared with the experimental data of two-state water reported in literature, and good agreements between them were demonstrated. This study offers a new physical insight into free volume for the anomalous dynamics and LLPTs in the two-state water.

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液-液相变过程中过冷水大分子异常动力学的双态自由体积模型

由于复杂液态水具有各种凝聚分子结构和相关的液-液相变（LLPT），因此对其异常动力学建模是一项巨大的挑战。在本研究中，我们首次考虑了自由体积和熵对低密度液态水（LDL）和高密度液态水（HDL）LLPT 的影响。首先，我们提出了双态自由体积模型，并结合 Adam-Gibbs 模型研究了双态水中的自由扩散系数、粘度、玻璃化转变温度和反常动态平衡。然后建立了自由能方程，以探讨自由体积、熵和异常动力学行为的构成关系。最后，将所提出的双态自由体积模型的分析结果与文献报道的双态水实验数据进行了比较，结果表明两者之间具有良好的一致性。这项研究为自由体积在双态水中的反常动力学和 LLPTs 提供了新的物理视角。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Chemical Physics Letters 化学-物理：原子、分子和化学物理

CiteScore

5.70

自引率

3.60%

发文量

798

审稿时长

33 days

期刊介绍： Chemical Physics Letters has an open access mirror journal, Chemical Physics Letters: X, sharing the same aims and scope, editorial team, submission system and rigorous peer review. Chemical Physics Letters publishes brief reports on molecules, interfaces, condensed phases, nanomaterials and nanostructures, polymers, biomolecular systems, and energy conversion and storage. Criteria for publication are quality, urgency and impact. Further, experimental results reported in the journal have direct relevance for theory, and theoretical developments or non-routine computations relate directly to experiment. Manuscripts must satisfy these criteria and should not be minor extensions of previous work.