An Investigation in the Kinetic Persistence of TiO$_2$ Polymorphs using Machine Learning Driven Pathfinding in Crystal Configuration Space

Abstract

As the number of theoretically predicted materials continues to grow, it becomes increasingly important to assess not only their thermodynamic stability but also their kinetic viability under realistic synthesis conditions. In this study, we investigate the hypothesis that the kinetic persistence of a metastable polymorph is related to the topography of the potential energy landscape separating it from lower energy phases. To accomplish this, we develop a new method for identifying diffusionless transformation pathways between metastable polymorphs and their ground-state counterparts and discuss the energetics of those pathways with respect to the experimental observation of each phase. This algorithm is underpinned by the recently developed Crystal Normal Form, which provides a graph representation of crystal configuration space and supplies the substrate for our pathfinding algorithm. We apply this method to the titanium dioxide system which contains the well-known anatase, rutile, and brookite phases in addition to a number of hypothetical metastable polymorphs.