Multiconfiguration Pair-Density Functional Theory with Quantum Embedding Predicts Correct CO Adsorption Sites on...

Area of Science:

• Computational Chemistry
• Materials Science
• Surface Science

Background:

• Carbon monoxide (CO) adsorption on copper is crucial for heterogeneous catalysis and CO2 reduction.
• Standard density-functional theory (DFT) methods struggle to accurately predict CO binding sites and energies on copper.
• Existing functionals like PBE and M06-L incorrectly favor hollow sites over experimentally observed on-top sites for CO on copper.

Purpose of the Study:

• To develop and validate a computational method for accurate prediction of CO adsorption on copper facets.
• To identify the correct lowest-energy binding sites and adsorption energies of CO on various copper surfaces.
• To overcome the limitations of traditional DFT functionals in modeling CO-copper interactions.

Main Methods:

• Application of quantum embedded multiconfiguration pair-density functional theory (emb-MC-PDFT).
• Integration of the PBE functional within the emb-MC-PDFT framework.
• First-principles calculations for CO adsorption on copper (111), (110), and (100) facets.

Main Results:

• emb-MC-PDFT correctly predicts the most favorable binding sites for CO on copper (111), (110), and (100) facets.
• Accurate quantitative prediction of CO adsorption energies on these copper surfaces.
• Resolution of the discrepancy between theoretical predictions and experimental observations regarding CO binding sites.

Conclusions:

• Quantum embedded multiconfiguration pair-density functional theory (emb-MC-PDFT) provides a reliable approach for studying CO adsorption on copper.
• This method accurately determines CO binding energies and identifies the correct binding sites, crucial for understanding copper-mediated catalysis.
• emb-MC-PDFT offers a significant advancement over standard DFT functionals for modeling catalytic intermediates and reaction mechanisms.