Interface-Limited Growth of Heterogeneously Nucleated Ice in Supercooled Water

Abstract

Heterogeneous ice growth exhibits a maximum in freezing rate arising from the competition between kinetics and the thermodynamic driving force between the solid and liquid states. Here, we use molecular dynamics simulations to elucidate the atomistic details of this competition, focusing on water properties in the interfacial region along the secondary prismatic direction. The crystal growth velocity is maximized when the efficiency of converting interfacial water molecules to ice, collectively known as the attachment kinetics, is greatest. We find water molecules that contact the intermediate ice layer in concave regions along the atomistically roughened surface are more likely to freeze directly. An increased roughening of the solid surface at large undercoolings consequently plays an important limiting role in the rate of ice growth, as water molecules are unable to integrate into increasingly deeper surface pockets. These results provide insight into the molecular mechanisms for self-assembly of solid phases that are important in many biological and atmospheric processes.