Ice Formation on Kaolinite: Insights from Molecular Dynamics Simulations

Abstract

The formation of ice affects many aspects of our everyday life as well as technologies such as cryotherapy and cryopreservation. Foreign substances almost always aid water freezing through heterogeneous ice nucleation, but the molecular details of this process remain largely unknown. In fact, insight into the microscopic mechanism of ice formation on different substrates is difficult to obtain even via state-of-the-art experimental techniques. At the same time, atomistic simulations of heterogeneous ice nucleation frequently face extraordinary challenges due to the complexity of the water-substrate interaction and the long timescales that characterize nucleation events. Here, we have investigated several aspects of molecular dynamics simulations of heterogeneous ice nucleation considering as a prototypical ice nucleating material the clay mineral kaolinite, which is of relevance in atmospheric science. We show via seeded molecular dynamics simulations that ice nucleation on the hydroxylated (001) face of kaolinite proceeds exclusively via the formation of the hexagonal ice polytype. The critical nucleus size is two times smaller than that obtained for homogeneous nucleation at the same supercooling. Previous findings suggested that the flexibility of the kaolinite surface can alter the time scale for ice nucleation within molecular dynamics simulations. However, we here demonstrate that equally flexible (or non flexible) kaolinite surfaces can lead to very different outcomes in terms of ice formation, according to whether or not the surface relaxation of the clay is taken into account. We show that very small structural changes upon relaxation dramatically alter the ability of kaolinite to provide a template for the formation of a hexagonal overlayer of water molecules at the water-kaolinite interface, and that this relaxation therefore determines the nucleation ability of this mineral.

References in corpus (19)

• Canonical sampling through velocity-rescaling
• Escaping free-energy minima
• Crystal Nucleation in Liquids: Open Questions and Future Challenges in Molecular Dynamics Simulations
• Forward Flux Sampling for rare event simulations
• Ice structures, patterns, and processes: A view across the ice-fields
• Homogeneous ice nucleation at moderate supercooling from molecular simulation
• Direct Calculation of Ice Homogeneous Nucleation Rate for a Molecular Model of Water
• The Many Faces of Heterogeneous Ice Nucleation: Interplay Between Surface Morphology and Hydrophobicity
• Crystal nucleation of hard spheres using molecular dynamics, umbrella sampling and forward flux sampling: A comparison of simulation techniques
• Homogeneous ice nucleation evaluated for several water models
• Relation between Rotational and Translational Dynamic Heterogeneities in Water
• Ice Nucleation on Carbon Surface Supports the Classical Theory for Heterogeneous Nucleation
• Microscopic Mechanism and Kinetics of Ice Formation at Complex Interfaces: Zooming in on Kaolinite
• The Microscopic Features of Heterogeneous Ice Nucleation May Affect the Macroscopic Morphology of Atmospheric Ice Crystals
• Suppression of Sub-surface Freezing in Free-Standing Thin Films of a Coarse-grained Model of Water
• Anharmonic nuclear motion and the relative stability of hexagonal and cubic ice
• Toward Accurate Adsorption Energetics on Clay Surfaces
• The Effect of Substrate on Thermodynamic and Kinetic Anisotropies in Atomic Thin Films
• Computational investigation of structure, dynamics and nucleation kinetics of a family of modified Stillinger-Weber model fluids in bulk and free-standing thin films

Cited by in corpus (17)

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• Unravelling the Origins of Ice Nucleation on Organic Crystals
• Seeding Approach to nucleation in the NVT ensemble: the case of bubble cavitation in overstretched Lennard Jones fluids
• Stabilization of AgI's polar surfaces by the aqueous environment, and its implications for ice formation
• Heterogeneous Seeded Molecular Dynamics as a Tool to Probe the Ice Nucleating Ability of Crystalline Surfaces
• Crystalline clusters in mW water: stability, growth, and grain boundaries
• Is the Local Ion Density Sufficient to Drive NaCl Nucleation from the Melt and Aqueous Solution?
• Communication: Truncated non-bonded potentials can yield unphysical behavior in molecular dynamics simulations of interfaces
• Macroscopic surface charges from microscopic simulations
• Simulations of water nano-confined between corrugated planes
• Effect of substrate mismatch, orientation, and flexibility on heterogeneous ice nucleation
• A Fully Quantum-Mechanical Treatment for Kaolinite
• Can molecular simulations reliably compare homogeneous and heterogeneous ice nucleation?
• Effect of Interfacial Dipole on Heterogeneous Ice Nucleation
• Robustness of classical nucleation theory to chemical heterogeneity of crystal nucleating substrates
• Heterogeneous ice nucleation on model substrates
• The Effect of Dipole from $\gamma$-AgI Substrates on Heterogeneous Ice Nucleation