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dc.contributor.authorBuehl, Michael
dc.contributor.authorReimann, Christoph
dc.contributor.authorPantazis, Dimitrios A.
dc.contributor.authorBredow, Thomas
dc.contributor.authorNeese, Frank
dc.date.accessioned2011-03-31T16:01:02Z
dc.date.available2011-03-31T16:01:02Z
dc.date.issued2008-09
dc.identifier.citationBuehl , M , Reimann , C , Pantazis , D A , Bredow , T & Neese , F 2008 , ' Geometries of third-row transition-metal complexes from density-functional theory ' , Journal of Chemical Theory and Computation , vol. 4 , no. 9 , pp. 1449-1459 . https://doi.org/10.1021/ct800172jen
dc.identifier.issn1549-9618
dc.identifier.otherPURE: 5311542
dc.identifier.otherPURE UUID: e2f78e1a-34f7-4351-b7cb-0f9c24524254
dc.identifier.otherWOS: 000259091400005
dc.identifier.otherScopus: 58149236843
dc.identifier.otherORCID: /0000-0002-1095-7143/work/48131784
dc.identifier.urihttp://hdl.handle.net/10023/1756
dc.description.abstractA set of 41 metal-ligand bond distances in 25 third-row transition-metal complexes, for which precise structural data are known in the gas phase, is used to assess optimized and zero-point averaged geometries obtained from DFT computations with various exchange-correlation functionals and basis sets. For a given functional (except LSDA) Stuttgart-type quasi-relativistic effective core potentials and an all-electron scalar relativistic approach (ZORA) tend to produce very similar geometries. In contrast to the lighter congeners, LSDA affords reasonably accurate geometries of 5d-metal complexes, as it is among the functionals with the lowest mean and standard deviations from experiment. For this set the ranking of some other popular density functionals, ordered according to decreasing standard deviation, is BLYP > VSXC > BP86 approximate to BPW91 approximate to TPSS approximate to B3LYP approximate to PBE > TPSSh > B3PW91 approximate to B3P86 approximate to PBE hybrid. In this case hybrid functionals are superior to their nonhybrid variants. In addition, we have reinvestigated the previous test sets for 3d- (Buhl M.; Kabrede, H. J. Chem. Theory Comput. 2006, 2, 1282-1290) and 4d- (Waller, M. P.; Buhl, M. J. Comput. Chem. 2007,28,1531-1537) transition-metal complexes using all-electron scalar relativistic DFT calculations in addition to the published nonrelativistic and ECP results. For this combined test set comprising first-, second-, and third-row metal complexes, B3P86 and PBE hybrid are indicated to perform best. A remarkably consistent standard deviation of around 2 pm in metal-ligand bond distances is achieved over the entire set of d-block elements.
dc.format.extent11
dc.language.isoeng
dc.relation.ispartofJournal of Chemical Theory and Computationen
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 DOI: 10.1021/ct800172jen
dc.subjectPhase electron-diffractionen
dc.subjectGeneralized gradient approximationen
dc.subjectZeta-valence qualityen
dc.subjectGaussian-basis setsen
dc.subjectMolecular equilibrium structuresen
dc.subjectOrder regular approximationen
dc.subjectEffective core potentialsen
dc.subjectFirst born approximationen
dc.subjectMain-group elementsen
dc.subjectKohn-sham theoryen
dc.subjectQD Chemistryen
dc.subject.lccQDen
dc.titleGeometries of third-row transition-metal complexes from density-functional theoryen
dc.typeJournal articleen
dc.description.versionPostprinten
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.identifier.doihttps://doi.org/10.1021/ct800172j
dc.description.statusPeer revieweden


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