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Title: Geometries of third-row transition-metal complexes from density-functional theory
Authors: Buehl, Michael
Reimann, Christoph
Pantazis, Dimitrios A.
Bredow, Thomas
Neese, Frank
Keywords: Phase electron-diffraction
Generalized gradient approximation
Zeta-valence quality
Gaussian-basis sets
Molecular equilibrium structures
Order regular approximation
Effective core potentials
First born approximation
Main-group elements
Kohn-sham theory
QD Chemistry
Issue Date: Sep-2008
Citation: Buehl , 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 . , 10.1021/ct800172j
Abstract: A 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.
Version: Postprint
Status: Peer reviewed
ISSN: 1549-9618
Type: Journal article
Rights: This 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/ct800172j
Appears in Collections:University of St Andrews Research
Chemistry Research

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