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

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    Author
    Perdew, John P.; Sun, Jianwei; Garza, Alejandro J.; Scuseria, Gustavo E.
    Date
    2016
    Abstract
    The 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.
    Citation
    Perdew, John P., Sun, Jianwei, Garza, Alejandro J., et al.. "Intensive Atomization Energy: Re-Thinking a Metric for Electronic Structure Theory Methods." Zeitschrift für Physikalische Chemie, 230, no. 5-7 (2016) De Gruyter: 737-742. http://dx.doi.org/10.1515/zpch-2015-0713.
    Published Version
    http://dx.doi.org/10.1515/zpch-2015-0713
    Keyword
    DFT; atomization energies; intensive variables; extensive variables; standard benchmark; More... chemical accuracy Less...
    Type
    Journal article
    Publisher
    De Gruyter
    Citable link to this page
    https://hdl.handle.net/1911/90584
    Rights
    Article 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.
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    • Chemistry Publications [636]
    • Faculty Publications [4988]
    • Physics and Astronomy Publications [1771]

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    Managed by the Digital Scholarship Services at Fondren Library, Rice University
    Physical Address: 6100 Main Street, Houston, Texas 77005
    Mailing Address: MS-44, P.O.BOX 1892, Houston, Texas 77251-1892
    Site Map