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.
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28 July 2022
Research Article|
August 01 2022
Intermolecular forces at ice and water interfaces: Premelting, surface freezing, and regelation
Special Collection:
Fluids Meet Solids
Juan Luengo-Márquez
;
Juan Luengo-Márquez
(Data curation, Formal analysis, Investigation, Software, Visualization, Writing – review & editing)
1
Department of Theoretical Condensed Matter Physics and Instituto Nicolás Cabrera, Universidad Autónoma de Madrid
, 28049 Madrid, Spain
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Fernando Izquierdo-Ruiz
;
Fernando Izquierdo-Ruiz
(Data curation, Methodology, Software, Validation, Visualization)
2
Departamento de Química-Física y Analítica, Facultad de Ciencias Químicas, Universidad de Oviedo
, 33006 Oviedo, Spain
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Luis G. MacDowell
Luis G. MacDowell
a)
(Conceptualization, Formal analysis, Funding acquisition, Investigation, Project administration, Resources, Supervision, Validation, Writing – original draft, Writing – review & editing)
3
Departamento de Química-Física, Facultad de Ciencias Químicas, Universidad Complutense de Madrid
, 28040 Madrid, Spain
a)Author to whom correspondence should be addressed: lgmac@quim.ucm.es
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a)Author to whom correspondence should be addressed: lgmac@quim.ucm.es
Note: This paper is part of the JCP Special Topic on Fluids Meets Solids.
J. Chem. Phys. 157, 044704 (2022)
Article history
Received:
April 28 2022
Accepted:
July 04 2022
Citation
Juan Luengo-Márquez, Fernando Izquierdo-Ruiz, Luis G. MacDowell; Intermolecular forces at ice and water interfaces: Premelting, surface freezing, and regelation. J. Chem. Phys. 28 July 2022; 157 (4): 044704. https://doi.org/10.1063/5.0097378
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