A complete description of thermodynamic stabilities of molecular crystals

Abstract

Significance Predicting stable polymorphs of molecular crystals remains one of the grand challenges of computational science. Current methods invoke approximations to electronic structure and statistical mechanics and thus fail to consistently reproduce the delicate balance of physical effects determining thermodynamic stability. We compute the rigorous ab initio Gibbs free energies for competing polymorphs of paradigmatic compounds, using machine learning to mitigate costs. The accurate description of electronic structure and full treatment of quantum statistical mechanics allow us to predict the experimentally observed phase behavior. This constitutes a key step toward the first-principles design of functional materials for applications from photovoltaics to pharmaceuticals.