Geometries of third-row transition-metal complexes from density-functional theory

Michael Buehl, Christoph Reimann, Dimitrios A. Pantazis, Thomas Bredow, Frank Neese

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346 Citations (Scopus)


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.

Original languageEnglish
Pages (from-to)1449-1459
Number of pages11
JournalJournal of Chemical Theory and Computation
Issue number9
Early online date22 Aug 2008
Publication statusPublished - Sept 2008


  • 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


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