冰水界面动态结构的分子动力学模拟研究

doi:10.11949/0438-1157.20211479

摘要/Abstract

摘要：

为了探究结冰过程冰水界面结构的动态复杂性，利用分子动力学模拟方法构建微观的冰水两相共存模型，研究了冰水两相界面结构随温度和晶面的变化规律。结果表明，当冰水两相达到平衡时，冰水界面结构中存在无序水分子和有序冰晶结构的可逆动态转变，造成了界面结构的不均匀性。在改变环境温度和晶面类型时，冰水界面结构表现出不同的分布规律。在相同的温度下，一次棱柱面和二次棱柱面的界面层厚度比基面的略薄，而棱柱面水分子排列的有序性强，且存在分子间氢键的三维网络重组。当过冷度较大时，界面结构趋于六元环排列的有序状态，界面内无序水分子增多，同时水分子在界面层内的停留时间增长。从分子尺度上阐明了冰水体系界面结构的变化规律，对理解结冰过程和发展控冰技术具有一定的指导意义。

关键词: 分子模拟, 冰水界面, 动态结构, 序参量, 结冰

Abstract:

A microcosmic model of ice-water two-phase was constructed by molecular dynamics simulation method, and the variation of interface structure with temperature and interface structures was studied. The results show that when two phases reach equilibrium, there is a reversible dynamic transition between the disordered water molecules and the ordered ice crystals at interface, which results in the dynamics of the interface structure. The ice-water interface structure is largely dependent on temperature and crystal planes. At the same temperature, the interface thickness of primary prism and secondary prism is slightly thinner than that of the base plane, and the boundary is well-organized and three-dimensional network recombination of intermolecular hydrogen bonds exists. When the degree of supercooling increases, the interface structure tends to the ordered state of six-membered ring arrangement, and the number of disorder water molecules in the interface increases. The residence time of water molecules at the interface layer increases, and the probability of crystal plane growth increases.This article clarified the change law of the interface structure of ice-water system from the molecular scale, which has certain guiding significance for understanding the icing process and the development of ice control technology.

Key words: molecular simulation, interface of ice and water, dynamic structure, order parameters, icing

中图分类号:

TS 01

王瑞, 任瑛, 陈卫, 韩永生. 冰水界面动态结构的分子动力学模拟研究[J]. 化工学报, 2022, 73(3): 1315-1323.

Rui WANG, Ying REN, Wei CHEN, Yongsheng HAN. Molecular dynamics simulation on the dynamic structure of icing interface[J]. CIESC Journal, 2022, 73(3): 1315-1323.

图/表 7

图1 采用序参量表征冰晶生长过程中冰水界面微观结构的动态变化过程(a)；液态水、冰水共存和固态冰晶体系分子结构及其水分子序参量概率分布曲线(b)

Fig.1 The complex dynamic process of the interface microstructure in the process of ice crystal growth in liquid water characterized by order parameters (a); The structure of liquid water, ice-water and ice crystal with probability distribution curve (PDC) of order parameters for water molecules (b)

图2 不同温度下体系的氧-氧径向分布函数对比

Fig.2 Comparison of the radial distribution function gO—O(r) of the system at different temperatures

图3 不同时间冰水界面处水分子结构(a)；冰水界面示意图(b)；两相平衡态时界面处类冰水分子数目随时间的变化(c)

Fig.3 The structures of the ice-water interface at different time (a); Schematic diagram of the ice-water interface (b); The number of ice-like water molecules changes with times at the two-phase equilibrium condition (c)

图4 不同温度下体系水分子序参量概率分布曲线：（a）降温过程；（b）升温过程

Fig.4 Probability distribution curve (PDC) of order parameters at different temperatures: (a) cooling process; (b) heating process

图5 在不同温度下二次棱柱面{112ˉ0}的界面密度剖面图

Fig.5 Density profile of the ice-water interface formed by secondary prismatic plane 112ˉ0

图6 不同晶面形成的冰水两相体系的序参量概率分布曲线，数字分别代表类冰水分子（右）和类液水分子（左）数目

Fig.6 Probability distribution curve (PDC) of the order parameters in ice-water system formed by three different crystal planes, and the figures in the histogram represent the number of water molecules at liquid (left) and solid phases (right), respectively

图7 不同晶面形成的冰水界面的密度剖面图

Fig.7 Density profile of the ice-water interface formed at different crystal planes

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