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    Troubles in the systematic prediction of transition metal thermochemistry with contemporary out-of-the-box methods

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    Type
    Article
    Authors
    Minenkov, Yury cc
    Chermak, Edrisse cc
    Cavallo, Luigi cc
    KAUST Department
    Physical Sciences and Engineering (PSE) Division
    KAUST Catalysis Center (KCC)
    Date
    2016-03-22
    Permanent link to this record
    http://hdl.handle.net/10754/603695
    
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    Abstract
    The recently developed DLPNO-CCSD(T) method and 7 popular DFT functionals (B3LYP, M06, M06L, PBE, PBE0, TPSS and TPSSh) with and without an empirical dispersion term have been tested to reproduce 111 gas phase reaction enthalpies involving 11 different transition metals. Our calculations, corrected for both relativistic effects and basis set incompleteness, indicate that most of the methods applied with default settings perform with acceptable accuracy on average. Nevertheless, our calculations also evidenced unexpected and non systematic large deviations for specific cases. For group 12 metals (Zn, Cd, Hg) most of the methods provided mean unsigned errors (MUE) less than 5.0 kcal/mol, with DLPNO-CCSD(T) and PBE methods performing excellently (MUE lower 2.0 kcal/mol). Problems started with group 4 metals (Ti and Zr). Best performer for Zr complexes with a MUE of 1.8 kcal/mol, PBE0-D3, provides a MUE larger than 8 kcal/mol for Ti. DLPNO-CCSD(T) provides a reasonable MUE of 3.3 kcal/mol for Ti reactions, but gives MUE a larger than 14.4 kcal/mol for Zr complexes, with all the larger deviations for reactions involving ZrF4. Large and non-systematic errors have been obtained for group 6 metals (Mo and W), for 8 reactions containing Fe, Cu, Nb and Re complexes. Finally, for the whole set of 111 reactions, the DLPNO-CCSD(T), B3LYP-D3 and PBE0-D3 methods turned out to be the best performers, both providing MUE below 5.0 kcal/mol. Since DFT results cannot be systematically improved and large non-systematic deviations of 20-30 kcal/mol were obtained even for best performers, our results indicates that current DFT methods are still unable to provide robust predictions in transition metal thermochemistry, at least for the functionals explored in this work. The same conclusion holds for both DLPNO-CCSD(T) and canonical CCSD(T) methods when used entirely as out-of-the-box. However if careful investigation core correlation is performed, relativistic effects are properly included and the quality of the reference wave function is properly checked, CCSD(T) methods can still provide good quality results that might be even used to validate DFT methods, due to paucity of accurate thermodynamic data for realistic-size transition metal complexes.
    Citation
    Troubles in the systematic prediction of transition metal thermochemistry with contemporary out-of-the-box methods 2016 Journal of Chemical Theory and Computation
    Sponsors
    We gratefully acknowledge Dr. Valery V. Sliznev, Ivanovo State University of Chemistry and Technology, The Russian Federation and Prof. Dr. Takeshi Noro, Hokkaido University, Japan for helpful discussions and correspondence. We also gratefully acknowledge Prof. Dr. José A. Martinho Simões, University of Lisbon, Portugal for providing us the original references on formation enthalpies of some organometallic species published on NIST webbook. The research reported in this publication was supported by funding from King Abdullah University of Science and Technology (KAUST). For computer time, this research used the resources of the Supercomputing Laboratory at King Abdullah University of Science and Technology (KAUST) in Thuwal, Saudi Arabia.
    Publisher
    American Chemical Society (ACS)
    Journal
    Journal of Chemical Theory and Computation
    ISSN
    1549-9618
    1549-9626
    DOI
    10.1021/acs.jctc.5b01163
    PubMed ID
    27002380
    Additional Links
    http://pubs.acs.org/doi/abs/10.1021/acs.jctc.5b01163
    ae974a485f413a2113503eed53cd6c53
    10.1021/acs.jctc.5b01163
    Scopus Count
    Collections
    Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

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