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Title: 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,23, 5048 (1981)] self-interaction-correction(PZSIC), as well two variations of the recently developed, locally scaled self-interaction correction (LSIC) [Zope et al.,J. Chem. Phys.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 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. Furthermore, 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 roughy equal sizemore » for the non-hydrogen transfer reactions.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Texas, El Paso, TX (United States)
  2. Univ. of Pittsburgh, PA (United States)
  3. Central Michigan Univ., Mount Pleasant, MI (United States)
Publication Date:
Research Org.:
Central Michigan Univ., Mount Pleasant, MI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1837828
Alternate Identifier(s):
OSTI ID: 1838422; OSTI ID: 1838562
Grant/Contract Number:  
SC0018331
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 156; Journal Issue: 1; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Substitution reactions; Delocalization; Corrections; Quantum chemistry; Correlation energy; Density functional theory; Atom transfer reactions

Citation Formats

Mishra, Prakash, Yamamoto, Yoh, Johnson, J. Karl, Jackson, Koblar Alan, Zope, Rajendra R., and Baruah, Tunna. Study of self-interaction-errors in barrier heights using locally scaled and Perdew-Zunger self-interaction methods. United States: N. p., 2022. Web. doi:10.1063/5.0070893.
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Mishra, Prakash, Yamamoto, Yoh, Johnson, J. Karl, Jackson, Koblar Alan, Zope, Rajendra R., & Baruah, Tunna. Study of self-interaction-errors in barrier heights using locally scaled and Perdew-Zunger self-interaction methods. United States. https://doi.org/10.1063/5.0070893
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Mishra, Prakash, Yamamoto, Yoh, Johnson, J. Karl, Jackson, Koblar Alan, Zope, Rajendra R., and Baruah, Tunna. Thu . "Study of self-interaction-errors in barrier heights using locally scaled and Perdew-Zunger self-interaction methods". United States. https://doi.org/10.1063/5.0070893. https://www.osti.gov/servlets/purl/1837828.
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@article{osti_1837828,
title = {Study of self-interaction-errors in barrier heights using locally scaled and Perdew-Zunger self-interaction methods},
author = {Mishra, Prakash and Yamamoto, Yoh and Johnson, J. Karl and Jackson, Koblar Alan and Zope, Rajendra R. and Baruah, Tunna},
abstractNote = {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,23, 5048 (1981)] self-interaction-correction(PZSIC), as well two variations of the recently developed, locally scaled self-interaction correction (LSIC) [Zope et al.,J. Chem. Phys.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 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. Furthermore, 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 roughy equal size for the non-hydrogen transfer reactions.},
doi = {10.1063/5.0070893},
journal = {Journal of Chemical Physics},
number = 1,
volume = 156,
place = {United States},
year = {Thu Jan 06 00:00:00 EST 2022},
month = {Thu Jan 06 00:00:00 EST 2022}
}
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