Comparative assessment of density functional methods for 3d transition-metal chemistry.
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 (Sc(2), Ni(2), and V(2)) 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.
Zhao
Yan
Y
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455-0431, USA.
Truhlar
Donald G
DG
D000465:Algorithms; D002627:Chemistry, Physical / Q000379:methods*; D005459:Fluorides / Q000737:chemistry; D006358:Hot Temperature; D006860:Hydrogen Bonding; D007700:Kinetics; D008024:Ligands; D008670:Metals / Q000737:chemistry*; D008956:Models, Chemical; D008962:Models, Theoretical; D010087:Oxides / Q000737:chemistry*; D012984:Software; D013696:Temperature; D028561:Transition Elements / Q000737:chemistry*
D008024:Ligands; D008670:Metals; D010087:Oxides; D028561:Transition Elements; D005459:Fluorides