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

TL;DR

This study evaluates the impact of self-interaction errors on chemical reaction barrier heights using PZSIC and locally scaled SIC methods, demonstrating improved accuracy over LDA, especially with the iso-orbital indicator scaling.

Contribution

It introduces and compares two variants of locally scaled self-interaction correction methods for better barrier height predictions in chemical reactions.

Findings

Both PZSIC and LSIC improve barrier height predictions over LDA.

LSIC with iso-orbital indicator z provides more consistent improvements.

Density-driven errors are significant in LDA reaction barrier calculations.

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.