ICAMS / Interdisciplinary Centre for Advanced Materials Simulation


Maximum likelihood analysis of reaction coordinates during solidification in Ni

G. Díaz Leines, J. Rogal.

The Journal of Physical Chemistry B, 122, 10934-10942, (2018)

Optimal reaction coordinate (RC) and free energy landscape for nucleation during crystallization in nickel. The transition path on the free energy landscape evidences a two-step mechanism where an initial formation of a prestructured liquid region precedes the crystal nucleation and has a key role in the description of the RC.

Understanding the underlying mechanism of crystal nucleation is a fundamental aspect in the prediction and control of materials properties. Classical nucleation theory (CNT) assumes that homogeneous nucleation occurs via random fluctuations within the supercooled liquid, that the structure of the growing clusters resembles the most stable bulk phase, and that the nucleus size is the sole reaction coordinate (RC) of the process. Many materials are, however, known to exhibit multiple steps during crystallization, forming different polymorphs. As a consequence, more complex RCs are often required to capture all relevant information about the process. Here, we employ transition path sampling together with a maximum likelihood analysis of candidate order parameters to identify suitable RCs for the nucleation mechanism during solidification in Ni. In contrast to CNT, the analysis of the reweighted path ensemble shows that a prestructured liquid region that surrounds the crystal cluster is a relevant order parameter that enhances the RC and therefore plays a key role in the description of the nucleus and the interfacial free energy. We demonstrate that prestructured liquid clusters that emerge within the liquid act as precursors of the crystallization in a nonclassical two-step mechanism, which predetermines the coordination of the selected polymorphs.

DOI: 10.1021/acs.jpcb.8b08718
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