Journal of Molecular Modeling

, Volume 14, Issue 3, pp 171–181 | Cite as

DFT tests for group 8 transition metal carbonyl complexes

  • Pipsa Hirva
  • Matti Haukka
  • Minna Jakonen
  • M. Andreina Moreno
Original Paper


The applicability of several popular density functionals in predicting the geometrical parameters and energetics of transition metal carbonyl complexes of iron, ruthenium and osmium has been studied. The methods tested include pure GGA functionals (BLYP, BP86, OPBE, HCTH, PBE, VSXC) and hybrid GGA functionals (B3PW91, B3LYP, PBE1PBE, MPW1K, B97-2, B1B95, PBE1KCIS). The effect of changing the metal basis set from Huzinaga’s all-electron basis to SDD scECP basis was also studied. The results show, that hybrid functionals are needed in order to describe the back-bonding ability of the carbonyl ligands as well as to deal with metal-metal bonds. The best general performance, when also the computational cost was considered, was obtained with hybrid functionals B3PW91 and PBE1PBE, which therefore provide an efficient tool for solving problems involving large or medium sized transition metal carbonyl compounds.


Optimized structure for one of the test molecules, the Ru3(CO)12 cluster, showing the staggered conformation of the carbonyl ligands


Density functional calculations Iron Osmium Ruthenium Transition metals 



Financial support from the Academy of Finland (P.H., M.J.) is gratefully acknowledged.


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Copyright information

© Springer-Verlag 2007

Authors and Affiliations

  • Pipsa Hirva
    • 1
  • Matti Haukka
    • 1
  • Minna Jakonen
    • 1
  • M. Andreina Moreno
    • 1
  1. 1.Department of ChemistryUniversity of JoensuuJoensuuFinland

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