Role of pre-ordered liquid in the selection mechanism of crystal polymorphs during nucleation

Abstract

We investigate the atomistic mechanism of homogeneous nucleation during solidification in molybdenum employing transition path sampling. The mechanism is characterized by the formation of a pre-structured region of high bond-orientational order in the supercooled liquid followed by the nucleation of the crystalline bulk phase within the center of the growing solid cluster. This precursor plays a crucial role in the process, as it provides a diffusive interface between the liquid and crystalline core, which lowers the interfacial free energy and facilitates the nucleation of the bulk phase. Furthermore, the structural features of the pre-ordered regions are distinct from the liquid and solid phases, and preselect the specific polymorph that nucleates. The similarity in the nucleation mechanism of Mo with that of metals that exhibit different crystalline bulk phases indicates that the formation of a precursor is a general feature observed in these materials. The strong influence of the structural characteristics of the precursors on the final crystalline bulk phase demonstrates that for the investigated system polymorph selection takes place in the very early stages of nucleation.

References in corpus (6)

• Accurate determination of crystal structures based on averaged local bond order parameters
• Crystal Nucleation in Liquids: Open Questions and Future Challenges in Molecular Dynamics Simulations
• Reaction rate calculation by parallel path swapping
• Systematic Improvement of Classical Nucleation Theory
• Crystal nucleation as the ordering of multiple order parameters
• Modification of the classical nucleation theory based on molecular simulation data for surface tension, critical nucleus size, and nucleation rate

Cited by in corpus (4)

• The Seven Deadly Sins: when computing crystal nucleation rates, the devil is in the details
• Template induced precursor formation in heterogeneous nucleation -- Controlling polymorph selection and nucleation efficiency
• Controlling crystallization: What liquid structure and dynamics reveal about crystal nucleation mechanisms
• Nucleation rates from small scale atomistic simulations and transition state theory