Maximum Likelihood Analysis of Reaction Coordinates during Solidification in Ni

TL;DR

This study uses transition path sampling and maximum likelihood analysis to identify key reaction coordinates in Ni solidification, revealing the importance of pre-structured liquid regions and a non-classical two-step nucleation mechanism.

Contribution

It introduces a novel approach combining transition path sampling with maximum likelihood analysis to identify complex reaction coordinates in Ni crystallization, challenging classical nucleation theory.

Findings

Pre-structured liquid regions are crucial reaction coordinates.

Crystallization proceeds via a non-classical two-step mechanism.

Pre-structured clusters influence polymorph selection.

Abstract

Understanding the underlying mechanism of crystal nucleation during solidification 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. In this work, we employ transition path sampling together with a maximum likelihood analysis of candidate order parameters to identify suitable reaction coordinates for the nucleation mechanism during solidification in Ni. In contrast to CNT, the analysis of the reweighted path ensemble shows that a pre-structured 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 growing nucleus and the interfacial free energy. We demonstrate that pre-structured liquid clusters that emerge within the liquid act as precursors of the crystallization in a non-classical two-step mechanism which predetermines the coordination of the polymorphs that are being selected.