Nonlocal functionals inspired by the strongly interacting limit of DFT: exact constraints and implementation

Abstract

Capturing strong correlation effects remains a key challenge for the development of improved exchange-correlation (XC) functionals in density functional theory. The recently proposed multiple radii functional (MRF) [J. Phys. Chem. Lett. 2017, 8, 2799; J. Chem. Theory Comput. 2019, 15, 3580] was designed to capture strong corre- lation effects seamlessly, as its mathematical structure draws from that of the exact XC functional in the limit of infinite correlations. The MRF functional provides a frame- work for building approximations along the density-fixed adiabatic connection, delivers accurate XC energy densities in the standard DFT gauge (same as that of the exact exchange energy density), and is free of one-electron self-interaction errors. To facilitate the development of XC functionals based on the MRF, we examine the behavior of the MRF functional when applied to uniform and scaled densities and consider how it can be made exact for the uniform electron gas. These theoretical insights are then used to build improved forms for the fluctuation function, an object that defines XC energy densities within the MRF framework. We also show how the MRF fluctuation function for physical correlation can be easily readjusted to accurately capture the XC functional in the limit of infinite correlations, demonstrating the versatility of MRF for building approximations for different correlation regimes. We describe the implementation of MRF using densities expanded on Gaussian basis sets, which improves the efficiency of previous grid-based MRF implementations. Finally, we present prospects for using the resulting MRF features for machine learning of XC approximations.