Free energy calculation of crystalline solids using normalizing flows

Abstract

Taking advantage of the advances in generative deep learning, particularly normalizing flow, a framework, called Boltzmann generator, has recently been proposed to generate equilibrium atomic configurations from the canonical ensemble and determining the associated free energy. In this work, we revisit Boltzmann generator to motivate the construction of the loss function from the statistical mechanical point of view and to cast the training of the normalizing flow model in a purely unsupervised manner that does not require any sample of the atomic configurations from the equilibrium ensemble. We further show that the normalizing flow framework furnishes a reference thermodynamic system, very close to the real thermodynamic system under consideration, that is suitable for the well-established free energy perturbation methods to determine accurate free energy of solids. We then apply the normalizing flow to two problems: temperature-dependent Gibbs free energy of perfect crystal and formation free energy of monovacancy defect in a model system of diamond cubic Si. The results obtained from the normalizing flow are shown to be in good agreement with that obtained from independent well-established free energy methods.