The fourth-order expansion of the exchange hole and neural networks to construct exchange–correlation functionals

Abstract

The curvature Q σ of spherically averaged exchange (X) holes ρX, σ(r, u) is one of the crucial variables for the construction of approximations to the exchange–correlation energy of Kohn–Sham theory, the most prominent example being the Becke–Roussel model [A. D. Becke and M. R. Roussel, Phys. Rev. A 39, 3761 (1989)]. Here, we consider the next higher nonzero derivative of the spherically averaged X hole, the fourth-order term T σ. This variable contains information about the nonlocality of the X hole and we employ it to approximate hybrid functionals, eliminating the sometimes demanding calculation of the exact X energy. The new functional is constructed using machine learning; having identified a physical correlation between T σ and the nonlocality of the X hole, we employ a neural network to express this relation. While we only modify the X functional of the Perdew–Burke–Ernzerhof functional [Perdew et al., Phys. Rev. Lett. 77, 3865 (1996)], a significant improvement over this method is achieved.