Vibrational Frequencies of Cerium Oxide-Bound CO: A Challenge for Conventional DFT Methods

TL;DR

This study reveals that conventional DFT methods fail to accurately predict vibrational frequencies of CO adsorbed on ceria surfaces, whereas hybrid DFT with HSE06 provides reliable results, aiding surface characterization.

Contribution

The paper demonstrates the limitations of standard DFT in modeling CO vibrational frequencies on ceria surfaces and shows that hybrid DFT with HSE06 yields better agreement with experiments.

Findings

Conventional DFT(PBE)+U does not reliably predict CO vibrational frequencies.

Hybrid DFT with HSE06 matches infrared spectroscopy data.

DFT inaccuracies are due to poor description of donation and backdonation effects.

Abstract

In ceria-based catalysis, the shape of the catalyst particle, which determines the exposed crystal facets, profoundly affects its reactivity. The vibrational frequency of adsorbed carbon monoxide (CO) can be used as a sensitive probe to identify the exposed surface facets, provided reference data on well-defined single crystal surfaces together with a definitive theoretical assignment exist. We investigate the adsorption of CO on the CeO2(110 and (111) surfaces and show that the commonly applied DFT(PBE)+U method does not provide reliable CO vibrational frequencies by comparing with state-of-the-art infrared spectroscopy experiments for monocrystalline CeO2 surfaces. Good agreement requires the hybrid DFT approach with the HSE06 functional. The failure of conventional DFT is explained in terms of its inability to accurately describe the facet- and configuration-specific donation and backdonation effects that control the changes in the C-O bond length upon CO adsorption and the CO force constant. Our findings thus provide a theoretical basis for the detailed interpretation of experiments and open up the path to characterize more complex scenarios, including oxygen vacancies and metal adatoms.