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)

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
4 Universidad de Alicante
5 iCLeHS - Institute of Chemistry for Life and Health Sciences
6 IUF - Institut universitaire de France

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.

Domaines: Chimie; Chimie théorique et/ou physique

Eric Brémond, Vincent Tognetti, Henry Chermette, Juan Carlos Sancho-García, Laurent Joubert, et al.. Electronic Energy and Local Property Errors at QTAIM Critical Points while Climbing Perdew’s Ladder of Density-Functional Approximations. Journal of Chemical Theory and Computation, 2022, pp.acs.jctc.1c00981. ⟨10.1021/acs.jctc.1c00981⟩. ⟨hal-03519879⟩