Evaluating Transition Metal Barrier Heights with the Latest Density Functional Theory Exchange–Correlation Functionals: The MOBH35 Benchmark Database

A new database of transition metal reaction barrier heights (MOBH35) is presented. Benchmark energies (forward and reverse barriers and reaction energy) are calculated using DLPNO-CCSD(T) extrapolated to the complete basis set limit using a Weizmann-1-like scheme. Using these benchmark energies, the performance of a wide selection of density functional theory (DFT) exchange-correlation functionals, including the latest from the Martin, Truhlar, and Head-Gordon groups, is evaluated. It was found, using the def2-TZVPP basis set, that the ωB97M-V (MAD 1.7 kcal/mol), ωB97M-D3BJ (MAD 1.9 kcal/mol), ωB97X-V (MAD 2.0 kcal/mol), and revTPSS0-D4 (MAD 2.2 kcal/mol) hybrid functionals are recommended. The double-hybrid functionals B2K-PLYP (MAD 1.7 kcal/mol) and revDOD-PBEP86-D4 (MAD 1.8 kcal/mol) also performed well, but this has to be balanced by their increased computational cost.