Comparative
Assessment of DFT Performances in Ru- and Rh-Promoted σ‑Bond
Activations
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Abstract
In this work, the performances of
19 density functional theory (DFT) methods are calibrated comparatively
on Ru- and Rh-promoted σ-bond (C–H, O–H, and H–H)
activations. DFT calibration reference is generated from explicitly
correlated coupled cluster CCSD(T)-F12 calculations, and the 4s4p
core–valence correlation effect of the two 4d platinum group
transition metals is also included. Generally, the errors of DFT methods
for calculating energetics of Ru-/Rh-mediated reactions appear to
correlate more with the magnitude of energetics itself than other
factors such as metal identity. For activation energy calculations,
the best performing functionals for both Ru and Rh systems are MN12SX
<
CAM-B3LYP < M06-L < MN12L < M06 < ωB97X < B3LYP
< LC-ωPBE (in the order of increasing mean unsigned deviations,
MUDs, of less than 2 kcal/mol). For reaction energy calculations,
best functionals with MUDs less than 2 kcal/mol are PBE0 < CAM-B3LYP
≈ N12SX. The effect of the DFT empirical dispersion correction
on the performance of the DFT methods is beneficial for most density
functionals tested in this work, reducing their MUDs to different
extents. After including empirical dispersion correction, ωB97XD,
B3LYP-D3, and CAM-B3LYP-D3 (PBE0-D3, B3LYP-D3, and ωB97XD) are
the three best performing DFs for activation energy (reaction energy)
calculations, from which B3LYP-D3 and ωB97XD can notably be
recommended uniformly for both the reaction energy and reaction barrier
calculations. The good performance of B3LYP-D3 in quantitative description
of the energetic trends further adds value to B3LYP-D3 and singles
this functional out as a reasonable choice in the Ru/Rh-promoted σ-bond
activation processes