Intensive Atomization Energy: Re-Thinking a Metric for Electronic Structure Theory Methods

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dc.citation.firstpage737
dc.citation.issueNumber7-May
dc.citation.journalTitleZeitschrift für Physikalische Chemie
dc.citation.lastpage742
dc.citation.volumeNumber230
dc.contributor.authorPerdew, John P.
dc.contributor.authorSun, Jianwei
dc.contributor.authorGarza, Alejandro J.
dc.contributor.authorScuseria, Gustavo E.
dc.date.accessioned2016-06-27T15:39:57Z
dc.date.available2016-06-27T15:39:57Z
dc.date.issued2016
dc.description.abstractThe errors in atomization energies (AE) of molecules have long been used to measure the errors of wavefunction or density functional methods for electronic structure calculations. In particular, the G3 set of Pople and collaborators (for sp-bonded molecules from the first rows of the periodic table) has become a standard benchmark for such methods. But the mean absolute error of AE tends to increase with increasing number Nat of atoms in a molecule. In fact, AE is an extensive variable, which diverges as Nat →∞. Here, as did Savin and Johnson 2015, we define an intensive atomization energy, IAE = AE/Nat or atomization energy per atom, which tends to the finite cohesive energy (per atom) of a large cluster or solid (Nat →∞). We find that the mean absolute error of the G3 molecular IAE from accurate density functionals remains close to 1 kcal/mol as the average molecular size increases. This makes it possible to estimate in advance the magnitude of the error in AE for a molecule similar to most of those in the G3 set. It also allows us identify the G3 “outlying molecules”, and to more directly compare the accuracy of a given functional for different kinds of molecules (such as those containing transition-metal atoms) to that for G3-type molecules, by removing the otherwise-uncontrolled size factor. Finally, we point out that the familiar concept of “chemical accuracy” needs to be qualified.
dc.identifier.citationPerdew, John P., Sun, Jianwei, Garza, Alejandro J., et al.. "Intensive Atomization Energy: Re-Thinking a Metric for Electronic Structure Theory Methods." <i>Zeitschrift für Physikalische Chemie,</i> 230, no. 5-7 (2016) De Gruyter: 737-742. http://dx.doi.org/10.1515/zpch-2015-0713.
dc.identifier.doihttp://dx.doi.org/10.1515/zpch-2015-0713
dc.identifier.urihttps://hdl.handle.net/1911/90584
dc.language.isoeng
dc.publisherDe Gruyter
dc.rightsArticle is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
dc.subject.keywordDFT
dc.subject.keywordatomization energies
dc.subject.keywordintensive variables
dc.subject.keywordextensive variables
dc.subject.keywordstandard benchmark
dc.subject.keywordchemical accuracy
dc.titleIntensive Atomization Energy: Re-Thinking a Metric for Electronic Structure Theory Methods
dc.typeJournal article
dc.type.dcmiText
dc.type.publicationpublisher version
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