Evaluation of Range-Separated Hybrid and Other Density Functional Approaches on TestSets Relevant for Transition Metal-Based Homogeneous Catalysts

摘要

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 accuratetreatments of reaction kinetics. Range-separated hybrid density functionals have been shown to accuratelypredict 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 fromconventional 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 forapplications to homogeneous catalysis. Our results also point to the importance of the correlation functionalin range-separated hybrids.