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

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Catalysis

Background:

• Ligand association/dissociation is crucial in transition metal-catalyzed reactions.
• Accurate electronic energies are vital for understanding these reactions.
• Existing methods using Gaussian-type basis sets and counterpoise corrections have limitations.

Purpose of the Study:

• To compute metal-ligand association energies for transition metal complexes.
• To evaluate the accuracy of multiwavelet calculations compared to traditional basis sets.
• To identify issues with counterpoise corrections in determining binding energies.

Main Methods:

• Employed high-precision multiwavelet calculations.
• Calculated metal-ligand association energies for 27 transition metal complexes.
• Compared multiwavelet results with Gaussian-type basis sets and counterpoise corrections.

Main Results:

• Counterpoise corrections often lead to underbinding, underestimating interaction energies.
• Counterpoise corrections are problematic for reactions involving chemical transformations.
• Multiwavelet calculations provide accurate electronic interaction energies, free from basis set errors.

Conclusions:

• Multiwavelet methods are a reliable alternative for calculating electronic interaction energies.
• This approach overcomes limitations associated with basis set superposition errors.
• Accurate energy calculations are essential for advancing transition metal catalysis research.