Electronic Energy and Local Property Errors at QTAIM Critical Points while Climbing Perdew’s Ladder of Density-Functional Approximations

Eric Brémond; Vincent Tognetti; Henry Chermette; Juan Carlos Sancho-García; Laurent Joubert; Carlo Adamo

doi:10.1021/acs.jctc.1c00981

Journal articles

Electronic Energy and Local Property Errors at QTAIM Critical Points while Climbing Perdew’s Ladder of Density-Functional Approximations

Eric Brémond ^{1, *} Vincent Tognetti ^{2, *} Henry Chermette ³ Juan Carlos Sancho-García ⁴ Laurent Joubert ² Carlo Adamo ^{5, 6}

* Corresponding author

1 ITODYS (UMR_7086) - Interfaces, Traitements, Organisation et Dynamique des Systèmes

2 COBRA - Chimie Organique et Bioorganique : Réactivité et Analyse

3 Chemometrics and Theoretical Chemistry - Chimiométrie et chimie théorique

ISA - Institut des Sciences Analytiques

4 Universidad de Alicante

5 iCLeHS - Institute of Chemistry for Life and Health Sciences

6 IUF - Institut Universitaire de France

Abstract : We investigate the relationships between electron-density and electronic-energy errors produced by modern exchange-correlation density-functional approximations belonging to all of the rungs of Perdew's ladder. To this aim, a panel of relevant (semi)local properties evaluated at critical points of the electron-density field (as defined within the framework of Bader's atoms-in-molecules theory) are computed on a large selection of molecular systems involved in thermodynamic, kinetic, and noncovalent interaction chemical databases using density functionals developed in a nonempirical and minimally and highly parametrized fashion. The comparison of their density-and energy-based performance, also discussed in terms of density-driven errors, casts light on the strengths and weaknesses of the most recent and efficient density-functional approximations.

Document type :

Journal articles

Domain :

Chemical Sciences

Chemical Sciences / Theoretical and/or physical chemistry

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https://hal.archives-ouvertes.fr/hal-03519879
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Submitted on : Monday, January 10, 2022 - 5:06:40 PM
Last modification on : Thursday, April 7, 2022 - 1:58:27 PM

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