Analyzing multistep homogeneous nucleation in vapor-to-solid transitions using molecular dynamics simulations

In this paper, we present multistep homogeneous nucleations in vapor-to-solid transitions as revealed by molecular dynamics simulations on Lennard-Jones molecules, where liquidlike clusters are created and crystallized. During a long, direct NVE (constant volume, energy, and number of molecules) involving the integration of (1.9-15)×106 molecules in up to 200 million steps (=4.3 μs), crystallization in many large, supercooled nanoclusters is observed once the liquid clusters grow to a certain size (∼800 molecules for the case of T≃0.5/k). In the simulations, we discovered an interesting process associated with crystallization: the solid clusters lost 2-5 % of their mass during crystallization at low temperatures below their melting temperatures. Although the crystallized clusters were heated by latent heat, they were stabilized by cooling due to evaporation. The clusters crystallized quickly and completely except at surface layers. However, they did not have stable crystal structures, rather they had metastable structures such as icosahedral, decahedral, face-centered-cubic-rich (fcc-rich), and hexagonal-close-packed-rich (hcp-rich). Several kinds of cluster structures coexisted in the same size range of ∼1000-5000 molecules. Our results imply that multistep nucleation is a common first stage of condensation from vapor to solid.