Nucleation and growth of polytypic-layered crystals from the network liquid zinc chloride

Abstract

The liquid to solid crystallization for zinc (II) chloride is studied by molecular dynamics computer simulation. The transition is unusual in that it involves a change from a three-dimensional network liquid structure to a pseudo-two-dimensional layered crystal. The crystallization events are observed from four distinct liquid starting configurations and are identified by reference to the time evolution of the system energetics and Bragg peaks associated with the cation layering. Order parameters and molecular graphics are applied to understand the transitions at an atomistic length scale. Mechanisms are presented for the initial layer growth, the coherent joining of the layered crystallites, and the destruction of high-energy grain boundaries. The growth kinetics are analyzed by defining times for catastrophic and critical nucleation. The final crystal structures are shown to have essentially random anion close-packed stacking sequences consistent with the large number of experimentally observed polytypic structures. The formation of grain boundary stacking faults is also observed.