Luengo-Márquez Juan, Izquierdo-Ruiz Fernando, MacDowell Luis G
Department of Theoretical Condensed Matter Physics and Instituto Nicolás Cabrera, Universidad Autónoma de Madrid, 28049 Madrid, Spain.
Departamento de Química-Física y Analítica, Facultad de Ciencias Químicas, Universidad de Oviedo, 33006 Oviedo, Spain.
J Chem Phys. 2022 Jul 28;157(4):044704. doi: 10.1063/5.0097378.
Using Lifshitz theory, we assess the role of van der Waals forces at interfaces of ice and water. The results are combined with measured structural forces from computer simulations to develop a quantitative model of the surface free energy of premelting films. This input is employed within the framework of wetting theory and allows us to predict qualitatively the behavior of quasi-liquid layer thickness as a function of ambient conditions. Our results emphasize the significance of vapor pressure. The ice-vapor interface is shown to exhibit only incomplete premelting, but the situation can shift to a state of complete surface melting above water saturation. The results obtained serve also to assess the role of subsurface freezing at the water-vapor interface, and we show that intermolecular forces favor subsurface ice nucleation only in conditions of water undersaturation. We show that ice regelation at ambient pressure may be explained as a process of capillary freezing, without the need to invoke the action of bulk pressure melting. Our results for van der Waals forces are exploited in order to gauge dispersion interactions in empirical point charge models of water.
利用列夫席兹理论，我们评估了范德华力在冰与水界面处的作用。研究结果与计算机模拟测得的结构力相结合，以建立预熔膜表面自由能的定量模型。该输入应用于润湿理论框架内，使我们能够定性地预测准液层厚度随环境条件的变化情况。我们的研究结果强调了蒸气压的重要性。结果表明，冰 - 气界面仅表现出不完全预熔，但在水饱和以上，情况可能转变为完全表面熔化状态。所得结果还用于评估水汽界面处亚表面冻结的作用，我们表明，分子间力仅在水不饱和条件下有利于亚表面冰核的形成。我们表明，常压下的冰 regelation 可以解释为毛细管冻结过程，而无需援引体积压力熔化的作用。我们利用范德华力的研究结果来衡量水的经验点电荷模型中的色散相互作用。
