Direct evidence on the crossover from BCC to FCC stability: A lattice-based aggregation-volume-bias Monte Carlo approach to polymorphism.

Abstract

A lattice-based version of the aggregation-volume-bias Monte Carlo method that was introduced recently has allowed for the extension of the calculation of the nucleation free energies from liquid clusters to solid clusters. Here, it was used to calculate the nucleation free energies of both bcc and fcc clusters formed by Lennard-Jones particles. Under the simulation conditions considered in this study, a cross-over of the thermodynamic stability from the bcc to the fcc structure was observed directly from the free energy results. In addition, the free energies obtained for both types of clusters were used to extrapolate bulk phase information, including chemical potential and surface tension, which revealed that bcc clusters are favored due to the lower surface tension. These results corroborate a recent classical density functional theory study. This work also demonstrates that this approach can be used to predict the entire thermodynamic landscape (i.e., free energies for clusters of different structures and sizes, including an infinitely large cluster, which is the bulk phase), which is important to answer fundamental questions related to crystallization such as the origin of polymorphism.