Show simple item record

dc.contributor.authorJensen, Stig Rune
dc.contributor.authorSaha, Santanu
dc.contributor.authorFlores-Livas, Jose A
dc.contributor.authorHuhn, William
dc.contributor.authorBlum, Volker
dc.contributor.authorGoedecker, Stefan
dc.contributor.authorFrediani, Luca
dc.date.accessioned2018-08-02T12:59:11Z
dc.date.available2018-08-02T12:59:11Z
dc.date.issued2017-03-14
dc.description.abstractUsing 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.en_US
dc.description.sponsorshipThe Swiss National Science Foundationen_US
dc.descriptionThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry Letters, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see <a href=https://doi.org/10.1021/acs.jpclett.7b00255> https://doi.org/10.1021/acs.jpclett.7b00255</a>.en_US
dc.identifier.citationJensen, 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. Journal of Physical Chemistry Letters, 8(7), 1449-1457. https://doi.org/10.1021/acs.jpclett.7b00255en_US
dc.identifier.cristinIDFRIDAID 1543019
dc.identifier.doi10.1021/acs.jpclett.7b00255
dc.identifier.issn1948-7185
dc.identifier.urihttps://hdl.handle.net/10037/13340
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.journalJournal of Physical Chemistry Letters
dc.relation.projectIDinfo:eu-repo/grantAgreement/RCN/SFF/179568/Norway/Centre for Theoretical and Computational Chemistry/CTCC/en_US
dc.rights.accessRightsopenAccessen_US
dc.subjectVDP::Matematikk og Naturvitenskap: 400::Kjemi: 440en_US
dc.subjectVDP::Mathematics and natural science: 400::Chemistry: 440en_US
dc.titleThe Elephant in the Room of Density Functional Theory Calculationsen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


File(s) in this item

Thumbnail

This item appears in the following collection(s)

Show simple item record