Prediction of the Crystal Morphology of β‑HMX using a Generalized Interfacial Structure Analysis Model

At sufficiently low supersaturations such that the spiral growth mechanism dominates, β-cyclotetramethylenetetranitramine (HMX) grows from acetone into a polyhedron surrounded mainly by the (020) and (011) faces. In order to elucidate the morphology, a generalized form of the interfacial structure analysis model is suggested. In this method, the molecular order parameters of crystals are defined to identify the orientation and conformation of the adsorbed growth unit at the interface. This presents a robust method to calculate the orientational and conformational free energy surfaces that are utilized for the spiral growth model of centrosymmetric growth units with polygonal spiral edges. From the metadynamics simulation using these order parameters as collective variables, the free energy surfaces with respect to the collective variables revealed that high conformational free energy of the chair conformation discouraged preordering of the growth units into crystal-like orientation and conformation. The resulting morphology was consistent with the previous experimental and theoretical results, indicating that the anisotropic local concentrations of the growth units at the interface play a critical role in the different relative growth rates of the slow-growing faces