A Look at Real‐World Transition‐Metal Thermochemistry and Kinetics with Local Hybrid Functionals

Local hybrid functionals (LHs) use a position-dependent admixture of exact exchange in real space, which has previously been shown to offer various advantages over global hybrids and the potential construct with wide applicability. While main-group thermochemistry kinetics other properties have already studied extensively, no broad systematic investigation for energetics transition-metal complexes reported so far LHs. To close this gap, we evaluate eight LHs three test sets on barrier heights reaction energies real-world transition metal complexes, comparison several rung-4 functionals. The recent LH20t-D4 method emerges as top-performing functional overall benchmark, comparable simpler TPSS0-D4 slightly before more complex range-separated ωB97M-V. But ωB97M-V perform much better energetics, making them reliable tools study organometallic mechanisms. Given also its observed excellent performance mixed-valence systems, is thus widely applicable both chemistry, while providing convincing accuracy many spectroscopic properties. earlier LH14t-calPBE-D4 local performs well, some first-generation fall behind.