title: How Accurate Can a Local Coupled Cluster Approach Be in Computing the Activation Energies of Late-Transition-Metal-Catalyzed Reactions with Au, Pt, and Ir?
abstract: To improve the accuracy of local coupled cluster (LCC) methods in computing activation energies, we propose herein a new computational scheme. Its applications to various types of late-transition-metal-catalyzed reactions involving Au, Pt, and Ir indicate that the new corrective approach for LCC methods can downsize the mean unsigned deviation and maximum deviation, from the CCSD(T)/CBS reference, to about 0.3 and 0.9 kcal/mol. Using this method, we also calibrated the performance of popular density functionals, with respect to the same test set of reactions. It is concluded that the best functional is the general-purpose double hybrid functional B2GP-PLYP. Other well-performing functionals include the "kinetic" functionals M06-2X and BMK, which have a large percentage of HF exchange, and general-purpose functionals like PBE0 and wB97X. Comparatively, general-purpose functionals like PBE0 and TPSSh perform much better than the tested "kinetic" functionals for Pt-/Ir-catalyzed reactions, while the opposite is true for Au-catalyzed reactions. In contrast, wB97X performs more uniformly in these two classes of reactions. These findings hint that even within the scope of late transition metals, different types of reactions may require different types of optimal DFT methods. Empirical dispersion correction of DFT was found to have a small or no effect on the studied reactions barriers.
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
authors.forename: Runhua
authors.initials: R
authors.lastname: Kang
authors.affiliation: Department of Chemistry, Renmin University of China, Beijing, 100872, China.
authors.forename: Wenzhen
authors.initials: W
authors.lastname: Lai
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
authors.forename: Jiannian
authors.initials: J
authors.lastname: Yao
authors.affiliation: Institute of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Hebrew University of Jerusalem, Givat Ram Campus, 91904 Jerusalem, Israel.
authors.forename: Sason
authors.initials: S
authors.lastname: Shaik
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
authors.forename: Hui
authors.initials: H
authors.lastname: Chen