Comparative assessment of density functional methods for 3d transition-metal chemistry

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Abstract

In the present study, we comparatively assessed the newly developed M05 functional against a data set of reaction energies for transition-metal chemistry. The functionals to which we compare are BLYP, B3LYP, B97-2, MPWLYP1M, TPSS, and TPSSh. We draw the following conclusions: (1) TPSS gives the best performance for calculating the binding energies of three transition-metal dimers (Sc2, Ni2, and V2) that have severe multireference character, (2) B97-2 gives the best performance for calculating the binding energies of the nine metal-ligand diatomics (three monohydrides, three monoxide, and three monofluorides), and (3) M05 gives the overall best performance for all 18 data in the assessment, and it has a mean unsigned error 55% lower than the popular B3LYP functional. Since the M05 functional also gives good performance for main-group thermochemistry, for noncovalent chemistry, and for calculating barrier heights, M05 can be applied to a wide range of problems where nonhybrid functionals or functionals designed for kinetics fail.

Original languageEnglish (US)
Article number224105
JournalJournal of Chemical Physics
Volume124
Issue number22
DOIs
StatePublished - Jun 14 2006

Bibliographical note

Funding Information:
The authors are grateful to Nathan Schultz for many helpful discussions. This work was supported in part by the U.S. Department of Energy, Office of Basic Energy Sciences and in part by the Office of Naval Research under Grant No. N00012-05-01-0538.

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