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

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.

Automated summary

This study investigates the relationships between electron-density and electronic-energy errors produced by modern exchange-correlation density-functional approximations, and explores the strengths and weaknesses of the most recent and efficient density-functional approximations through comparison of their performance in terms of density- and energy-based errors on a large selection of molecular systems.