Kohn-Sham accuracy from orbital-free density functional theory via $Δ$-machine learning

Abstract

We present a $Δ$-machine learning model for obtaining Kohn-Sham accuracy from orbital-free density functional theory (DFT) calculations. In particular, we employ a machine learned force field (MLFF) scheme based on the kernel method to capture the difference between Kohn-Sham and orbital-free DFT energies/forces. We implement this model in the context of on-the-fly molecular dynamics simulations, and study its accuracy, performance, and sensitivity to parameters for representative systems. We find that the formalism not only improves the accuracy of Thomas-Fermi-von Weizs{ä}cker (TFW) orbital-free energies and forces by more than two orders of magnitude, but is also more accurate than MLFFs based solely on Kohn-Sham DFT, while being more efficient and less sensitive to model parameters. We apply the framework to study the structure of molten Al$_{0.88}$Si$_{0.12}$, the results suggesting no aggregation of Si atoms, in agreement with a previous Kohn-Sham study performed at an order of magnitude smaller length and time scales.