Vibrational Recognition of Adsorption Sites for Carbon Monoxide on Platinum and Platinum-Ruthenium Surfaces

Abstract

We have studied the vibrational properties of CO adsorbed on platinum and platinum-ruthenium surfaces using density-functional perturbation theory within the Perdew-Burke-Ernzerhof generalized-gradient approximation. The calculated C-O stretching frequencies are found to be in excellent agreement with spectroscopic measurements. The frequency shifts that take place when the surface is covered with ruthenium monolayers are also correctly predicted. This agreement for both shifts and absolute vibrational frequencies is made more remarkable by the frequent failure of local and semilocal exchange-correlation functionals in predicting the stability of the different adsorption sites for CO on transition metal surfaces. We have investigated the chemical origin of the C-O frequency shifts introducing an orbital-resolved analysis of the force and frequency density of states, and assessed the effect of donation and backdonation on the CO vibrational frequency using a GGA + molecular U approach. These findings rationalize and establish the accuracy of density-functional calculations in predicting absolute vibrational frequencies, notwithstanding the failure in determining relative adsorption energies, in the strong chemisorption regime.

arXiv comment21 pages, 9 figures

References in corpus (7)

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• A linear response approach to the calculation of the effective interaction parameters in the LDA+U method
• The steady-state of heterogeneous catalysis, studied by first-principles statistical mechanics
• First-principles extrapolation method for accurate CO adsorption energies on metal surfaces
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• Koopmans' condition for density-functional theory
• Extended DFT+U+V method with on-site and inter-site electronic interactions
• CO adsorption on Pt induced Ge nanowires
• Resilience of gas-phase anharmonicity in the vibrational response of adsorbed carbon monoxide and breakdown under electrical conditions