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

Abstract

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 H2, 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. File list (3) download file view on ChemRxiv Manuscript_MWonTM_31012021.pdf (1.86 MiB) download file view on ChemRxiv Supporting Information_MWonTM_31012021.pdf (3.26 MiB) download file view on ChemRxiv ALL_GEOMETRIES.xyz (103.21 KiB)

Quantifying Intramolecular Basis Set Superposition Errors

“…The latter reflects the well-known fact that the 6-311G basis set is effectively only of DZP quality, despite it formally being a TZP style basis set. 48,62 Note that the pcseg and Def2 basis sets perform similarly at the HF level, but the pcseg has lower errors at the B3LYP, likely reflecting that the pcseg basis sets have been optimized specifically for DFT methods. Note also that the pcseg-3 basis set, being of QZP quality, is required to reduce the MaxAD below 1 kJ/mol at the B3LYP level.…”

“…BSSE is absent when using plane-wave basis functions, but replacing the core electrons by, e.g., a pseudopotential introduces an inherent limitation that is difficult to quantify, and the requirement of using large unit cells for medium-sized molecules makes this unattractive. Recent developments in the use of MRA applied to quantum chemistry, , however, have made it possible to generate precise reference values at both Hartree–Fock (HF) and DFT levels at computationally accessible costs. , In the present study, we quantify the magnitude of intramolecular BSSE for a selection of spatially different conformations for a deca-peptide at HF and DFT levels using a selection of standard Gaussian basis sets against reference multiresolution values and evaluate the performance of proposed correction schemes. Calibration studies of BSSE have often focused on small model systems, but the present 186-atom system can be considered as a real-case application.…”

Computational mechanistic study in organometallic catalysis: Why prediction is still a challenge

“…As we will show below, reliable comparison of competing reaction pathways remains challenging even with good‐quality DFT, 26 1 with different functionals at times leading to conflicting predictions, 27 but experimental insights and/or calibration against calculations at higher levels of theory may serve to tension the data where DFT accuracy alone is uncertain or insufficient. Furthermore, as recently highlighted by Brakestad et al 28 calculations of this type have an error associated with the basis set. This basis set error results from two factors.…”

Importance profiles. Visualization of atomic basis set requirements

“…As already hinted above, fully numerical methods (see [1] for a recent review) allow the direct determination of CBS limit total energies and wave functions for Hartree-Fock, density functional theory [40,41], as well as for complete active space self-consistent field calculations, and are nowadays tractable for systems of appreciable size [42][43][44][45]. All-electron calculations have recently become feasible with plane waves, as well, through the use of a regularized nuclear Coulomb potential [46,47].…”