The secret role of water's structure near surfaces in ice formation

IF 9.4 1区 化学 Q1 CHEMISTRY, PHYSICAL
Gang Sun , Hajime Tanaka
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引用次数: 0

Abstract

Hypothesis

Most ice on Earth forms via heterogeneous nucleation, as homogeneous nucleation requires significant supercooling. Despite its prevalence, the microscopic mechanisms behind this process remain unclear. We hypothesize that ice nucleation is primarily driven by low-dimensional structural preordering in interfacial liquid layers, rather than by the surface's direct affinity for bulk ice.

Simulations

To test this hypothesis, we perform molecular dynamics simulations of ice nucleation on a simple cubic substrate with tunable hydrophilicity. We analyze layering, hydrogen-bond distortions, orientational order, and substrate-ice lattice matching to uncover the physical mechanisms that control nucleation pathways.

Findings

Bilayer hexagonal ice forms on all substrates, but the nucleation pathway depends sensitively on surface hydrophilicity. At low hydrophilicity, bylayer ice nucleates directly from interfacial water. As hydrophilicity increases, enhanced planarity and density promote sequential nucleation, with two-dimensional ice forming first in the contact layer, then in the second layer. Excessive hydrophilicity hinders this process by suppressing 2D ordering in the contact layer, reversing the nucleation sequence. Consequently, the nucleation rate is maximized at intermediate hydrophilicity. Furthermore, we find that crystalline preordering in the contact layer is strongest when the substrate lattice closely matches that of ice, minimizing the free energy barrier for nucleation. These results highlight how surface-induced liquid ordering — rather than simple templating — controls ice formation. This mechanism likely extends to tetrahedral liquids such as silicon, germanium, carbon, and silica, underscoring the universal role of interfacial liquid structuring in surface-assisted crystallization across natural and technological systems.

Abstract Image

水的结构在冰形成过程中的秘密作用。
假设:地球上的大多数冰是通过非均相成核形成的,因为均相成核需要明显的过冷。尽管它很普遍,但这一过程背后的微观机制仍不清楚。我们假设冰的成核主要是由界面液体层中的低维结构预先排序驱动的,而不是由表面对大块冰的直接亲和力驱动的。模拟:为了验证这一假设,我们在一个具有可调亲水性的简单立方基质上进行了冰核的分子动力学模拟。我们分析了分层、氢键扭曲、取向顺序和基质-冰格匹配,以揭示控制成核途径的物理机制。发现:在所有底物上都能形成双层六边形冰,但成核途径敏感地依赖于表面亲水性。在低亲水性下,层冰直接由界面水成核。随着亲水性的增加,平面度和密度的增强促进了顺序成核,首先在接触层形成二维冰,然后在第二层形成。过度的亲水性通过抑制接触层中的二维有序,逆转成核顺序来阻碍这一过程。因此,在中间亲水性时成核速率最大。此外,我们发现当衬底晶格与冰晶格紧密匹配时,接触层中的晶体预序最强,使成核的自由能垒最小。这些结果强调了表面诱导的液体有序——而不是简单的模板——是如何控制冰的形成的。这种机制可能延伸到四面体液体,如硅、锗、碳和二氧化硅,强调了界面液体结构在自然和技术系统中表面辅助结晶中的普遍作用。
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
CiteScore
16.10
自引率
7.10%
发文量
2568
审稿时长
2 months
期刊介绍: The Journal of Colloid and Interface Science publishes original research findings on the fundamental principles of colloid and interface science, as well as innovative applications in various fields. The criteria for publication include impact, quality, novelty, and originality. Emphasis: The journal emphasizes fundamental scientific innovation within the following categories: A.Colloidal Materials and Nanomaterials B.Soft Colloidal and Self-Assembly Systems C.Adsorption, Catalysis, and Electrochemistry D.Interfacial Processes, Capillarity, and Wetting E.Biomaterials and Nanomedicine F.Energy Conversion and Storage, and Environmental Technologies
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