Skip to main content
Journal cover image

The Elephant in the Room of Density Functional Theory Calculations.

Publication ,  Journal Article
Jensen, SR; Saha, S; Flores-Livas, JA; Huhn, W; Blum, V; Goedecker, S; Frediani, L
Published in: The journal of physical chemistry letters
April 2017

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.

Duke Scholars

Altmetric Attention Stats
Dimensions Citation Stats

Published In

The journal of physical chemistry letters

DOI

EISSN

1948-7185

ISSN

1948-7185

Publication Date

April 2017

Volume

8

Issue

7

Start / End Page

1449 / 1457

Related Subject Headings

  • 51 Physical sciences
  • 34 Chemical sciences
  • 03 Chemical Sciences
  • 02 Physical Sciences
 

Citation

APA
Chicago
ICMJE
MLA
NLM
Jensen, S. R., Saha, S., Flores-Livas, J. A., Huhn, W., Blum, V., Goedecker, S., & Frediani, L. (2017). The Elephant in the Room of Density Functional Theory Calculations. The Journal of Physical Chemistry Letters, 8(7), 1449–1457. https://doi.org/10.1021/acs.jpclett.7b00255
Jensen, Stig Rune, Santanu Saha, José A. Flores-Livas, William Huhn, Volker Blum, Stefan Goedecker, and Luca Frediani. “The Elephant in the Room of Density Functional Theory Calculations.The Journal of Physical Chemistry Letters 8, no. 7 (April 2017): 1449–57. https://doi.org/10.1021/acs.jpclett.7b00255.
Jensen SR, Saha S, Flores-Livas JA, Huhn W, Blum V, Goedecker S, et al. The Elephant in the Room of Density Functional Theory Calculations. The journal of physical chemistry letters. 2017 Apr;8(7):1449–57.
Jensen, Stig Rune, et al. “The Elephant in the Room of Density Functional Theory Calculations.The Journal of Physical Chemistry Letters, vol. 8, no. 7, Apr. 2017, pp. 1449–57. Epmc, doi:10.1021/acs.jpclett.7b00255.
Jensen SR, Saha S, Flores-Livas JA, Huhn W, Blum V, Goedecker S, Frediani L. The Elephant in the Room of Density Functional Theory Calculations. The journal of physical chemistry letters. 2017 Apr;8(7):1449–1457.
Journal cover image

Published In

The journal of physical chemistry letters

DOI

EISSN

1948-7185

ISSN

1948-7185

Publication Date

April 2017

Volume

8

Issue

7

Start / End Page

1449 / 1457

Related Subject Headings

  • 51 Physical sciences
  • 34 Chemical sciences
  • 03 Chemical Sciences
  • 02 Physical Sciences