CO adsorption on Pt(111) studied by periodic coupled cluster theory

Area of Science:

• Computational chemistry
• Surface science
• Materials science

Background:

• Understanding molecule-surface interactions is crucial for catalysis.
• Accurate theoretical methods are needed to predict adsorption behavior.
• Platinum surfaces are important in many catalytic processes.

Purpose of the Study:

• To apply periodic coupled-cluster theory to calculate CO adsorption energies on Pt(111).
• To investigate the accuracy of the CCSD(cT) method for adsorption energies.
• To determine the contributions of different energy components to CO binding.

Main Methods:

• Periodic coupled-cluster theory, specifically the CCSD(cT) ansatz.
• Calculation of correlation and Hartree-Fock energies for Pt surfaces with and without CO.
• Assessment of k-mesh convergence and basis set incompleteness errors.

Main Results:

• CCSD(cT) accurately predicts the relative adsorption energies for different CO adsorption sites on Pt(111).
• Hartree-Fock contributions dominate CO binding at the top site.
• Correlation energy contributions are significant for the fcc adsorption site.

Conclusions:

• Periodic coupled-cluster theory, particularly CCSD(cT), is a reliable method for studying adsorption phenomena.
• The study provides insights into the electronic structure governing CO-Pt interactions.
• Accurate theoretical predictions can guide the design of catalytic materials.