Evaluation of range-separated hybrid and other density functional approaches on test sets relevant for transition metal-based homogeneous catalysts.
Homogeneous catalysis by transition metal complexes is challenging to model with electronic structure theory. This is due to the large system sizes encountered, the wide range of bonding motifs, and the need for accurate treatments of reaction kinetics. Range-separated hybrid density functionals have been shown to accurately predict a variety of properties in (organic) main group chemistry. Here we benchmark representative range-separated hybrids for geometric and energetic properties of transition metal complexes. Results from conventional semilocal and global hybrid approaches are included for comparison. The range-separated hybrids' performance, combined with their demonstrated accuracy for main group kinetics, makes them promising for applications to homogeneous catalysis. Our results also point to the importance of the correlation functional in range-separated hybrids.
Jiménez-Hoyos
Carlos A
CA
Department of Chemistry, Rice University, Houston, Texas 77005, USA.
Janesko
Benjamin G
BG
Scuseria
Gustavo E
GE