Performance of Density Functional Theory for Transition Metal Oxygen Bonds

Klaus August Moltved, Kasper Planeta Kepp*

*Corresponding author for this work

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The accuracy of Density functional theory (DFT) limits predictions in theoretical catalysis, and strong chemical bonds between transition metals and oxygen pose a particular challenge. We benchmarked 30 diverse density functionals against the bond dissociation enthalpies (BDE) of the 30 MO and 30 MO+ diatomic systems of all the 3d, 4d, and 5d metals, to test universality across the d-block as required in comparative studies. Seven functionals, B98, B97-1, B3P86, B2PLYP, TPSSh, B3LYP, and B97-2, display mean absolute errors (MAE) <30 kJ/mol. In contrast, many commonly used functionals such as PBE and RPBE overestimate M-O bonding by +30 kJ/mol and display MAEs from 48-76 kJ/mol. RPBE and OPBE reduce the over-binding of PBE but remain very inaccurate. We identify a linear relationship (p-value 7.6·10-5 ) between the precision and accuracy of DFT, i.e. inaccurate functionals tend to produce larger, unpredictable random errors. Some functionals commonly deviate from this relationship: Thus, M06-2X is very precise but not very accurate, whereas B3LYP* and MN15-L are more accurate but less precise than M06-2X. The best-performing hybrids have 10-30% HF exchange, but this can be relieved by double hybrids (B2PLYP). Most functionals describe trends well, but errors comparing 5d to 4d/3d are ~10 kJ/mol larger than group-wise errors, due to uncertainties in the spin-orbit coupling corrections for effective core potentials, affecting e.g. Pt/Pd or Au/Ag comparisons.
Original languageEnglish
Issue number23
Pages (from-to)3210-3220
Number of pages11
Publication statusPublished - 2019


  • DFT
  • Transition metals
  • Oxygen
  • Catalysis
  • Bond dissociation enthalpy


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