流体机械

Interaction between Neighboring Supercritical Water Molecules and Density Fluctuation by Molecular Dynamics Simulations

  • WANG Yan ,
  • XU Jinliang ,
  • MA Xiaojing
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  • 1. Key Laboratory of Condition Monitoring and Control for Power Plant Equipment of Ministry of Education, North China Electric Power University, Beijing 102206, China
    2. Beijing Key Laboratory of Multiphase Flow and Heat Transfer, North China Electric Power University, Beijing 102206, China

网络出版日期: 2023-12-01

基金资助

This work was supported by the National Natural Science Foundation of China (51821004).

版权

Science Press, Institute of Engineering Thermophysics, CAS and Springer-Verlag GmbH Germany, part of Springer Nature 2022

Interaction between Neighboring Supercritical Water Molecules and Density Fluctuation by Molecular Dynamics Simulations

  • WANG Yan ,
  • XU Jinliang ,
  • MA Xiaojing
Expand
  • 1. Key Laboratory of Condition Monitoring and Control for Power Plant Equipment of Ministry of Education, North China Electric Power University, Beijing 102206, China
    2. Beijing Key Laboratory of Multiphase Flow and Heat Transfer, North China Electric Power University, Beijing 102206, China

Online published: 2023-12-01

Supported by

This work was supported by the National Natural Science Foundation of China (51821004).

Copyright

Science Press, Institute of Engineering Thermophysics, CAS and Springer-Verlag GmbH Germany, part of Springer Nature 2022

摘要

超临界水(supercritical Water, scW)在各种工程应用中具有重要意义,scW的结构和分布特征是控制相关过程和现象的关键。本文中,控制压力和温度,采用分子动力学(molecular dynamic, MD)模拟的方法研究了scW的动力学特性。观察到模拟盒子中心厚度为10 Å的区域内密度的振荡,这表明颗粒在局部区域的界面上进行质量交换。通过研究发现,低密度的scW表现出更强的非均匀性。通过均方根误差和最大结构因子两个参数对局部密度的波动进行了定量分析,且两种方法得到的结果具有较强的一致性。通过xz平面的密度二维分布可以发现,scW分子在局部紧密聚集形成“液岛”,但在其它区域会非常稀疏,类似于亚临界压力下的气液混合物。跟踪目标分子的平动和转动,发现前者显示出大幅度的弹道(扩散)运动和小幅度振荡,后者则显示出两个角度的跳跃尺度。平移和旋转运动都与氢键的断裂和重组有关。低密度scW分子间的氢键较少,多以孤立分子存在,而高密度scW则存在更多通过氢键组合在一起的分子簇。两个尺度的运动将对超临界状态下的热/化学过程产生影响,加深对scW结构的基本认识。

本文引用格式

WANG Yan , XU Jinliang , MA Xiaojing . Interaction between Neighboring Supercritical Water Molecules and Density Fluctuation by Molecular Dynamics Simulations[J]. 热科学学报, 2022 , 31(3) : 907 -922 . DOI: 10.1007/s11630-022-1574-0

Abstract

Supercritical water (scW) is important for various engineering applications. The structure and distribution of scW is key to dominate the related processes and phenomena. Here, scW is investigated using molecular dynamics (MD) simulation with controlled pressure and temperature. Density oscillation is observed to occur in a 1 nm thickness bin, indicating mass exchange of particles across the bin interface. We show that the low density scW behaves strong heterogeneity. Quantitative analysis of system density fluctuations is performed by square root error and maximum structure factor, demonstrating the agreement between the two methods. The scW molecules are tightly gathered to form “liquid island” locally, but are very sparse in other regions, which are similar to the gas-liquid mixture in subcritical pressure. A target molecule is tracked to plot 3D displacements and rotating angles, with the former indicating large amplitude ballistic (diffusing) motion and small amplitude oscillation, and the latter displaying two scales of angle jumping. Both translation and rotating motion are related to hydrogen bond break up and reorganization. The low density scW behaves isolated molecules with few combinations of hydrogen bonds between molecules, while the high density scW behaves more combinations of molecules via hydrogen bonds. The two scales motion is expected to influence thermal/chemical process in supercritical state, deepening the fundamental understanding of scW structure.

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