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

Abstract

Despite the great success that 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.

References in corpus (17)

• Climbing the Density Functional Ladder: Non-Empirical Meta-Generalized Gradient Approximation Designed for Molecules and Solids
• Localization and delocalization errors in density functional theory and implications for band-gap prediction
• Resolution-of-identity approach to Hartree-Fock, hybrid density functionals, RPA, MP2, and \textit{GW} with numeric atom-centered orbital basis functions
• Density functional theory in transition-metal chemistry: a self-consistent Hubbard U approach
• Fractional charge perspective on the band-gap in density-functional theory
• Koopmans' condition for density-functional theory
• Localized Orbital Scaling Correction for Systematic Elimination of Delocalization Error in Density Functional Approximations
• Delocalization errors in density functional theory are essentially quadratic in fractional occupation number
• Koopmans-compliant spectral functionals for extended systems
• Benefits of Range-separated Hybrid and Double-Hybrid Functionals for a Large and Diverse Dataset of Reaction Energies and Barrier Heights
• Approximating Quasiparticle and Excitation Energies from Ground State Generalized Kohn-Sham Calculations
• Transition state method and Wannier functions
• Localized orbital scaling correction for periodic systems
• Charge Transfer Excitation Energies From Ground State Density Functional Theory Calculations
• Combining Localized Orbital Scaling Correction and Bethe-Salpeter Equation for Accurate Excitation Energies
• Correcting Delocalization Error in Materials with Localized Orbitals and Linear-Response Screening
• Wannier Functions Dually Localized in Space and Energy