Performance of density functionals for first row transition metal systems

Kasper Planeta Kepp, Björn O. Roos, Ulf Ryde

Research output: Contribution to journalJournal articleResearchpeer-review


This article investigates the performance of five commonly used density functionals, B3LYP, BP86, PBE0, PBE, and BLYP, for studying diatomic molecules consisting of a first row transition metal bonded to H, F, Cl, Br, N, C, O, or S. Results have been compared with experiment wherever possible. Open-shell configurations are found more often in the order PBE0 > B3LYP > PBE similar to BP86 > BLYP. However, on average, 58 of 63 spins are correctly predicted by any functional, with only small differences. BP86 and PBE are slightly better for obtaining geometries, with errors of only 0.020 A. Hybrid functionals tend to overestimate bond lengths by a few picometers and underestimate bond strengths by favoring open shells. Nonhybrid functionals usually overestimate bond energies. All functionals exhibit similar errors in bond energies, between 42 and 53 kJ/mol. Late transition metals are found to be better modeled by hybrid functionals, whereas nonhybrid functionals tend to have less of a preference. There are systematic errors in predicting certain properties that could be remedied. BLYP performs the best for ionization potentials studied here, PBE0 the worst. In other cases, errors are similar. Finally, there is a clear tendency for hybrid functionals to give larger dipole moments than nonhybrid functionals. These observations may be helpful in choosing and improving existing functionals for tasks involving transition metals, and for designing new, improved functionals. (c) 2007 American Institute of Physics.
Original languageEnglish
Article number014103
JournalJournal of Chemical Physics
Issue number1
Publication statusPublished - 2007
Externally publishedYes


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