The Elephant in the Room of Density Functional Theory Calculations

• Published in: The journal of physical chemistry letters Vol. 8; no. 7; pp. 1449 - 1457
• Main Authors: Jensen, Stig Rune, Saha, Santanu, Flores-Livas, José A, Huhn, William, Blum, Volker, Goedecker, Stefan, Frediani, Luca
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 06.04.2017
• Subjects: Chemistry: 440; Kjemi: 440; Matematikk og Naturvitenskap: 400; Mathematics and natural science: 400; VDP
• DOI: 10.1021/acs.jpclett.7b00255
• ISSN: 1948-7185

Using multiwavelets, we have obtained total energies and corresponding atomization energies for the GGA-PBE and hybrid-PBE0 density functionals for a test set of 211 molecules with an unprecedented and guaranteed μHartree accuracy. These quasi-exact references allow us to quantify the accuracy of standard all-electron basis sets that are believed to be highly accurate for molecules, such as Gaussian-type orbitals (GTOs), all-electron numeric atom-centered orbitals (NAOs), and full-potential augmented plane wave (APW) methods. We show that NAOs are able to achieve the so-called chemical accuracy (1 kcal/mol) for the typical basis set sizes used in applications, for both total and atomization energies. For GTOs, a triple-ζ quality basis has mean errors of ∼10 kcal/mol in total energies, while chemical accuracy is almost reached for a quintuple-ζ basis. Due to systematic error cancellations, atomization energy errors are reduced by almost an order of magnitude, placing chemical accuracy within reach also for medium to large GTO bases, albeit with significant outliers. In order to check the accuracy of the computed densities, we have also investigated the dipole moments, where in general only the largest NAO and GTO bases are able to yield errors below 0.01 D. The observed errors are similar across the different functionals considered here.