Study of self-interaction-errors in barrier heights using locally scaled and Perdew-Zunger self-interaction methods

Abstract

We study the effect of self-interaction errors on the barrier heights of chemical reactions. For this purpose we use the well-known Perdew-Zunger [J. P. Perdew and A. Zunger, Phys. Rev. B, {\bf 23}, 5048 (1981)] self-interaction-correction (PZSIC), as well as two variations of the recently developed, locally scaled self-interaction correction (LSIC) [R. R. Zope \textit{et al.}, J. Chem. Phys. {\bf 151}, 214108 (2019)] to study the barrier heights of the BH76 benchmark dataset. Our results show that both PZSIC and especially the LSIC methods improve the barrier heights relative to the local density approximation (LDA). The version of LSIC that uses the iso-orbital indicator $z$ as a scaling factor gives a more consistent improvement than an alternative version that uses an orbital-dependent factor $w$ based on the ratio of orbital densities to the total electron density. We show that LDA energies evaluated using the self-consistent and self-interaction-free PZSIC densities can be used to assess density-driven errors. The LDA reaction barrier errors for the BH76 set are found to contain significant density-driven errors for all types of reactions contained in the set, but the corrections due to adding SIC to the functional are much larger than those stemming from the density for the hydrogen transfer reactions and of roughly equal size for the non-hydrogen transfer reactions.

arXiv comment11 pages, 2 figures

References in corpus (22)

• Localization and delocalization errors in density functional theory and implications for band-gap prediction
• Understanding and reducing errors in density functional calculations
• A critical assessment of the Self-Interaction Corrected Local Density Functional method and its algorithmic implementation
• Atomic self-interaction correction for molecules and solids
• Quantifying Density Errors in DFT
• The Importance of being consistent
• Self-interaction correction in multiple scattering theory
• The effect of the Perdew-Zunger self-interaction correction to density functionals on the energetics of small molecules
• Full self-consistency in Fermi-orbital self-interaction correction
• Fermi Orbital Derivatives in Self-Interaction Corrected Density Functional Theory: Applications to Closed Shell Atoms
• A step in the direction of resolving the paradox of Perdew-Zunger self-interaction correction
• Stretched or noded orbital densities and self-interaction correction in density functional theory
• Perdew-Zunger self-interaction correction: How wrong for uniform densities and large-Z atoms?
• Importance of self-interaction-error removal in density functional calculations on water cluster anions
• A Step in the Direction of Resolving the Paradox of Perdew-Zunger Self-interaction Correction. II. Gauge Consistency of the Energy Density at Three Levels of Approximation
• Improvements in the orbitalwise scaling down of Perdew-Zunger self-interaction correction in many-electron regions
• Fermi-Löwdin orbital self-interaction correction using the optimized effective potential method within the Krieger-Li-Iafrate approximation
• Improved Slater approximation to SIC-OEP
• Local self-interaction correction method with a simple scaling factor
• Static dipole polarizabilities of polyacenes using self-interaction-corrected density functional approximations
• Atomic Compton profiles within different exchange-only theories
• Implementation of Perdew-Zunger self-interaction correction in real space using Fermi-Löwdin orbitals

Cited by in corpus (4)

• Understanding density driven errors for reaction barrier heights
• Spin-state Gaps and Self-Interaction-Corrected Density Functional Approximations: Octahedral Fe(II) Complexes as Case Study
• Self-consistent implementation of locally scaled self-interaction-correction method
• The rise and fall of stretched bond errors: Extending the analysis of Perdew-Zunger self-interaction corrections of reaction barrier heights beyond the LSDA