Kinetics of Stacking Order Evolution During Heterogeneous Ice Formation

TL;DR

This study reveals the atomistic mechanisms of ice stacking order evolution during vapor deposition, showing a transition from cubic to hexagonal ice influenced by surface effects and symmetry considerations, supported by microscopy and simulations.

Contribution

It uncovers the dynamic process of stacking order transition in ice, integrating experimental cryo-EM observations with molecular dynamics simulations to explain crystallization preferences.

Findings

Recrystallization involves bifurcation from cubic to hexagonal ice.

Intermediate stacking-disordered layers act as a fluctuating bridge.

Surface effects and symmetry breaking influence ice crystallization.

Abstract

The selection of stacking order in a broad range of close-packed polymorphic materials remains a challenging enigma. Using in situ cryogenic transmission electron microscopy, we uncover the atomistic mechanisms governing the vapour deposition growth of ice. We find that the heterogeneous ice nucleation and growth undergoes recrystallization accompanied by bifurcation, reflecting a coherent epitaxial transition from a cubic-ice embryonic core to hexagonal-ice prismatic dendrites, with intermediate stacking-disordered layers serving as a dynamic fluctuating bridge. Supported by molecular dynamics simulations, these phenomena are attributed to a surface-constrained, symmetry-breaking crystallization preference aligned with the principle of minimizing free energy. Our results highlight the critical role of the combined effects of surface and symmetry in shaping ice crystallization, providing fresh insights into crystal growth mechanisms and guiding principles for the design of advanced materials.