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

Handle URI:
http://hdl.handle.net/10754/603695
Title:
Troubles in the systematic prediction of transition metal thermochemistry with contemporary out-of-the-box methods
Authors:
Minenkov, Yury; Chermak, Edrisse ( 0000-0002-2716-5724 ) ; Cavallo, Luigi ( 0000-0002-1398-338X )
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.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)
Citation:
Troubles in the systematic prediction of transition metal thermochemistry with contemporary out-of-the-box methods 2016 Journal of Chemical Theory and Computation
Publisher:
American Chemical Society (ACS)
Journal:
Journal of Chemical Theory and Computation
Issue Date:
22-Mar-2016
DOI:
10.1021/acs.jctc.5b01163
Type:
Article
ISSN:
1549-9618; 1549-9626
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.
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acs.jctc.5b01163
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorMinenkov, Yuryen
dc.contributor.authorChermak, Edrisseen
dc.contributor.authorCavallo, Luigien
dc.date.accessioned2016-03-27T12:26:45Zen
dc.date.available2016-03-27T12:26:45Zen
dc.date.issued2016-03-22en
dc.identifier.citationTroubles in the systematic prediction of transition metal thermochemistry with contemporary out-of-the-box methods 2016 Journal of Chemical Theory and Computationen
dc.identifier.issn1549-9618en
dc.identifier.issn1549-9626en
dc.identifier.doi10.1021/acs.jctc.5b01163en
dc.identifier.urihttp://hdl.handle.net/10754/603695en
dc.description.abstractThe 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.en
dc.description.sponsorshipWe 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.en
dc.language.isoenen
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acs.jctc.5b01163en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Chemical Theory and Computation, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.jctc.5b01163.en
dc.titleTroubles in the systematic prediction of transition metal thermochemistry with contemporary out-of-the-box methodsen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalJournal of Chemical Theory and Computationen
dc.eprint.versionPost-printen
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorMinenkov, Yuryen
kaust.authorChermak, Edrisseen
kaust.authorCavallo, Luigien
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