Anatomy of a complex crystallization pathway

Using molecular dynamics simulations, we investigate the crystallization pathways of two exemplary systems that form the same complex crystal structure but differ fundamentally in the nature of their particle interactions. One system is composed of point particles interacting via an isotropic pair potential characteristic of metallic compounds, while the other system contains hard polyhedra whose interactions arise from emergent entropic forces. Despite the stark difference in the origins of the particle interactions, we find that both systems are polymorphic and share the same crystal polymorphs. Moreover, the two systems follow the same multistep crystallization pathways. By examining the complex crystallization pathways on the single-particle level, we find that the local structure evolution of the two systems is also similar. Through mapping the hard particle system’s interaction to an effective Zetterling-like pairwise potential, we take a step toward understanding the origin of the observed similarities.