Multiwavelets applied to metal-ligand interactions: Energies free from basis set errors

Transition metal-catalyzed reactions invariably include steps where ligands associate or dissociate. In order to obtain reliable energies for such reactions, sufficiently large basis sets need to be employed. In this paper, we have used high-precision multiwavelet calculations to compute the metal-ligand association energies for 27 transition metal complexes with common ligands, such as H-2, CO, olefins, and solvent molecules. By comparing our multiwavelet results to a variety of frequently used Gaussian-type basis sets, we show that counterpoise corrections, which are widely employed to correct for basis set superposition errors, often lead to underbinding. Additionally, counterpoise corrections are difficult to employ when the association step also involves a chemical transformation. Multiwavelets, which can be conveniently applied to all types of reactions, provide a promising alternative for computing electronic interaction energies free from any basis set errors.

Automated summary

In this study, high-precision multiwavelet calculations were used to compute metal-ligand association energies for 27 transition metal complexes. The results showed that counterpoise corrections commonly used to correct for basis set superposition errors often lead to underbinding, especially when the association step involves a chemical transformation. Multiwavelets offer a promising alternative for computing electronic interaction energies free from any basis set errors, and can be conveniently applied to all types of reactions.