Molecular simulation of cross-nucleation between polymorphs.

Recent experiments report that an early nucleating crystalline structure (or polymorph) may nucleate another polymorph. We use molecular dynamics simulations to model this phenomenon known as cross-nucleation. We study the onset of crystallization in a liquid of Lennard-Jones particles cooled at a temperature 22% below the melting temperature. We show that growth proceeds through the successive cross-nucleation of the metastable hexagonal close-packed (hcp) polymorph on the stable face-centered cubic (fcc) polymorph and of the stable fcc polymorph on the metastable hcp polymorph. This finding is in agreement with the experimental results which demonstrated that the cross-nucleation of a stable polymorph on a metastable polymorph is just as likely as the cross-nucleation of a metastable polymorph on a stable polymorph. We then extend our findings established in the case of the homogeneous crystal nucleation to a situation of practical interest, i.e., when a seed of the stable polymorph is used. By studying the crystal growth from the (111) plane of a perfect fcc crystal, we show that, again, growth proceeds through the cross-nucleation of the hcp and fcc structures.