Coupled Cluster Benchmark of New Density Functionals and Domain Pair Natural Orbital Methods: Mechanisms of Hydroarylation and Oxidative Coupling Catalyzed by Ru(II) Chloride Carbonyls

TL;DR

This study evaluates the performance of new density functionals and domain pair natural orbital methods in modeling catalytic mechanisms involving Ru(II) chloride carbonyls, highlighting the effectiveness of DLPNO-CCSD(T) and recent functionals.

Contribution

It demonstrates that DLPNO-CCSD(T) can replace canonical CCSD(T) and shows the superior performance of recent functionals like {5}B97X-V and {5}B97M-V in catalytic studies.

Findings

DLPNO-CCSD(T) is an acceptable substitute for canonical CCSD(T).

Recent functionals {5}B97X-V and {5}B97M-V outperform traditional DFT functionals.

Revised DSD-PBEP86 double hybrid improves over the original, even for transition metal catalysis.

Abstract

In the present work, we tested the performance of several new functionals for studying the mechanisms of concurrent reaction of hydroarylation and oxidative coupling catalyzed by Ru(II) chloride carbonyls. We find that DLPNO-CCSD(T) is an acceptable substitute for full canonical CCSD(T) calculations; that the recent {\omega}B97X-V and {\omega}B97M-V functionals exhibit superior performance to commonly used DFT functionals; and that the revised DSD-PBEP86 double hybrid represents an improvement over the original, even though transition metals were not involved in its parametrization.