Leveraging normalizing flows for orbital-free density functional theory

Abstract

Abstract Orbital-free density functional theory (OF-DFT) for real-space systems has historically depended on Lagrange optimization techniques, primarily due to the inability of previously proposed electron density approaches to ensure the normalization constraint. This study illustrates how leveraging contemporary generative models, notably normalizing flows (NFs), can surmount this challenge. We develop a Lagrangian-free optimization framework by employing these machine learning models for the electron density. This diverse approach also integrates cutting-edge variational inference techniques and equivariant deep learning models, offering an innovative reformulation to the OF-DFT problem. We demonstrate the versatility of our framework by simulating a one-dimensional diatomic system, LiH, and comprehensive simulations of hydrogen, lithium hydride, water, and four hydrocarbon molecules. The inherent flexibility of NFs facilitates initialization with promolecular densities, markedly enhancing the efficiency of the optimization process.