Eliminating Delocalization Error through Localized Orbital Scaling Correction with Orbital Relaxation from Linear Response

TL;DR

This paper extends the linear response localized orbital scaling correction (lrLOSC) method to larger molecular systems, improving the accuracy of density functional theory calculations by effectively addressing delocalization errors across diverse chemical systems.

Contribution

The authors develop an efficient implementation of lrLOSC applicable to large molecules, demonstrating its effectiveness in correcting delocalization errors in a wide range of chemical systems.

Findings

Screening effect is crucial for large molecules' accuracy.

lrLOSC provides reliable results for organic and transition-metal systems.

Computational costs are comparable to standard KS-DFT calculations.

Abstract

Despite the great success Kohn-Sham density functional theory (KS-DFT) has achieved, the delocalization error remains a major challenge for commonly used density functional approximations (DFAs), resulting in systematic errors in ionization energies, electron affinities, band structures, and charge distributions. A recently developed localized orbital scaling correction (LOSC) method, namely linear response LOSC (lrLOSC), addresses these challenges by incorporating a functional correction that includes the screening effect and orbital localization within the LOSC framework. The method has been shown to provide accurate descriptions of bulk systems and core-level binding energies in small molecular systems. In this work, we extend the applicability of lrLOSC to a broader range of molecular systems, spanning various sizes, with a focus on the corrections to valence orbital energies and total energies. To enable the calculation of large chemical systems, we developed an efficient implementation of lrLOSC with computational costs comparable to standard KS-DFT calculations. Numerical results show that, while screening provides modest improvements for small molecules, it becomes critical for achieving high accuracy in larger molecules, from linear to three-dimensional systems. With the screening effect well captured in a unified way, lrLOSC provides accurate descriptions for a wide range of chemical systems, including organic molecular systems of varying sizes and transition-metal oxide complexes, establishing it as a powerful tool for enhancing the reliability of computational simulations of chemical systems.