olLOSC: Unified and efficient density functional approximation to correct delocalization error in molecules and periodic materials

Abstract

Density functional theory (DFT) is the most promising method for calculating quantum properties of molecules and materials at moderate and large scales. However, commonly used density functional approximations (DFAs) have systematic delocalization error, as demonstrated by underestimated band gaps, over-delocalized charges, and energy level misalignment at interfaces, which limits its quantitative prediction. Extensive efforts, such as the $GW$ approximation to many-body perturbation theory, system-specific tuning of DFA parameters, and correction functionals have been developed to address delocalization error. However, an accurate, efficient, and unified solution to describe total energy, charge density and band structure for both finite systems and materials is still not available. Building on the linear-response localized orbital scaling correction (lrLOSC), we introduce olLOSC: a localized orbital scaling correction with curvature calculated by orbital-free electronic linear response. olLOSC has comparable accuracy to lrLOSC, but is much more computationally efficient. olLOSC corrects delocalization error - especially underestimated gaps, but also the total energy - both in molecules and in materials with small and moderate band gaps, within the same orbital-free approximation. Critically, with a a unified approximation, olLOSC opens the path for robust and efficient DFT applications across molecules, materials, and interfaces.

Figures (1)

• Figure 1: DFA (blue) and olLOSC (orange) fundamental gaps (ionization potentials for polyacetylenes), in (a) molecules and polymers, (b) materials. Reference values are from (a) CCSD(T) and RASPT2, (b) experiments, corrected for zero-point renormalization. The orbitalet space/energy mixing parameter $\gamma = 0.30$, and the kinetic energy functional is $\text{TF} + 75\%\,\text{vW}$ ($\lambda = 0.75$).