Nucleation of crystals that are mixed composites of all three polymorphs in the Gaussian core model.

Abstract

We present results of computer simulations of homogeneous crystal nucleation in the Gaussian core model. In our simulations, we study the competition between the body-centered-cubic (bcc), face-centered-cubic (fcc), and hexagonal-close-packed crystal phases. We find that the crystal nuclei that form from the metastable fluid phase are typically "mixed"; they do not consist of a single crystal polymorph. Furthermore, when the fcc phase is stable or fcc and bcc phases are equally stable, this mixed nature is found to persist far beyond the size at the top of the nucleation barrier, that is, far into what would be considered the growth (rather than nucleation) regime. In this region, the polymorph that forms is therefore selected long after nucleation. This has implications. When nucleation is slow, it will be the rate-limiting step for crystallization. Then, the step that determines the time scale for crystallisation is different from the step that controls which polymorph forms. This means that they can be independently controlled. Also between nucleation and polymorph selection, there is a growing phase that is clearly crystalline not fluid, but this phase cannot be assigned to any one polymorph.