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Understanding Density-Driven Errors for Reaction Barrier Heights
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    Understanding Density-Driven Errors for Reaction Barrier Heights
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    • Aaron D. Kaplan*
      Aaron D. Kaplan
      Department of Physics, Temple University, Philadelphia, Pennsylvania19122, United States
      *Email: [email protected]
    • Chandra Shahi
      Chandra Shahi
      Department of Physics, Temple University, Philadelphia, Pennsylvania19122, United States
    • Pradeep Bhetwal
      Pradeep Bhetwal
      Department of Physics, Temple University, Philadelphia, Pennsylvania19122, United States
    • Raj K. Sah
      Raj K. Sah
      Department of Physics, Temple University, Philadelphia, Pennsylvania19122, United States
      More by Raj K. Sah
    • John P. Perdew*
      John P. Perdew
      Department of Physics, Temple University, Philadelphia, Pennsylvania19122, United States
      Department of Chemistry, Temple University, Philadelphia, Pennsylvania19122, United States
      *Email: [email protected]
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    Journal of Chemical Theory and Computation

    Cite this: J. Chem. Theory Comput. 2023, 19, 2, 532–543
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    https://doi.org/10.1021/acs.jctc.2c00953
    Published January 4, 2023
    Copyright © 2023 American Chemical Society

    Abstract

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    Delocalization errors, such as charge-transfer and some self-interaction errors, plague computationally efficient and otherwise accurate density functional approximations (DFAs). Evaluating a semilocal DFA non-self-consistently on the Hartree–Fock (HF) density is often recommended as a computationally inexpensive remedy for delocalization errors. For sophisticated meta-GGAs like SCAN, this approach can achieve remarkable accuracy. This HF-DFT (also known as DFA@HF) is often presumed to work, when it significantly improves over the DFA, because the HF density is more accurate than the self-consistent DFA density in those cases. By applying the metrics of density-corrected density functional theory (DFT), we show that HF-DFT works for barrier heights by making a localizing charge-transfer error or density overcorrection, thereby producing a somewhat reliable cancellation of density- and functional-driven errors for the energy. A quantitative analysis of the charge-transfer errors in a few randomly selected transition states confirms this trend. We do not have the exact functional and electron densities that would be needed to evaluate the exact density- and functional-driven errors for the large BH76 database of barrier heights. Instead, we have identified and employed three fully nonlocal proxy functionals (SCAN 50% global hybrid, range-separated hybrid LC-ωPBE, and SCAN-FLOSIC) and their self-consistent proxy densities. These functionals are chosen because they yield reasonably accurate self-consistent barrier heights and because their self-consistent total energies are nearly piecewise linear in fractional electron number─two important points of similarity to the exact functional. We argue that density-driven errors of the energy in a self-consistent density functional calculation are second order in the density error and that large density-driven errors arise primarily from incorrect electron transfers over length scales larger than the diameter of an atom.

    Copyright © 2023 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jctc.2c00953.

    • Validation tests of the methodology used in this work, formal derivation of the order of charge-transfer errors, and additional data and figures (PDF)

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    This article is cited by 18 publications.

    1. Andrew M. Wibowo-Teale, Bang C. Huynh, Trygve Helgaker, David J. Tozer. Classical Reaction Barriers in DFT: An Adiabatic-Connection Perspective. Journal of Chemical Theory and Computation 2025, 21 (1) , 124-137. https://doi.org/10.1021/acs.jctc.4c01038
    2. R.A.B. van Bree, G. J. Kroes. O2 Dissociation on Cu(111) Dynamics on a Novel Screened Hybrid van der Waals DFT Potential Energy Surface. The Journal of Physical Chemistry C 2024, 128 (45) , 19182-19196. https://doi.org/10.1021/acs.jpcc.4c05466
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    8. Priyanka B. Shukla, Prakash Mishra, Tunna Baruah, Rajendra R. Zope, Koblar A. Jackson, J. Karl Johnson. How Do Self-Interaction Errors Associated with Stretched Bonds Affect Barrier Height Predictions?. The Journal of Physical Chemistry A 2023, 127 (7) , 1750-1759. https://doi.org/10.1021/acs.jpca.2c07894
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    13. Yashpal Singh, Juan E. Peralta, Koblar A. Jackson. The rise and fall of stretched bond errors: Extending the analysis of Perdew–Zunger self-interaction corrections of reaction barrier heights beyond the LSDA. The Journal of Chemical Physics 2024, 160 (12) https://doi.org/10.1063/5.0179261
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    Journal of Chemical Theory and Computation

    Cite this: J. Chem. Theory Comput. 2023, 19, 2, 532–543
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jctc.2c00953
    Published January 4, 2023
    Copyright © 2023 American Chemical Society

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