Pablo G. Lustemberg^1,2*, Philipp Pleßow³, Yuemin Wang⁴, Chengwu Yang⁴, Alexei Nefedov⁴, Felix Studt³, Christof Wöll⁴, M. Verónica Ganduglia-Pirovano²

1 Institute of Physics Rosario, IFIR, National Scientific and Technical Research Council, CONICET, and National University of Rosario, UNR, S2000EKF Rosario, Santa Fe, Argentina

2 Institute of Catalysis and Petrochemistry, ICP, Spanish National Research Council, CSIC, 28049 Madrid, Spain

3 Institute of Catalysis Research and Technology, IKFT, Karlsruhe Institute of Technology, KIT, 76344 Eggenstein-Leopoldshafen, Germany

4 Institute of Functional Interfaces, IFG, Karlsruhe Institute of Technology, KIT, 76344 Eggenstein-Leopoldshafen, Germany

* Corresponding authors emails: lustemberg@gmail.com

DOI10.24435/materialscloud:z7-z0 [version v1]

Publication date: Aug 27, 2020

How to cite this record

Pablo G. Lustemberg, Philipp Pleßow, Yuemin Wang, Chengwu Yang, Alexei Nefedov, Felix Studt, Christof Wöll, M. Verónica Ganduglia-Pirovano, Vibrational frequencies of cerium oxide-bound CO: a challenge for conventional DFT methods, Materials Cloud Archive 2020.100 (2020), doi: 10.24435/materialscloud:z7-z0.

Description

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.

Materials Cloud sections using this data

Files

File name	Size	Description
HSE06.zip MD5md5:c4e8d6a5a55efa8a3f6e032111af57f2	3.4 MiB	DFT calculations of CO adsorption on CeO2 (111) and (110) with HSE06 functional
PBE0.zip MD5md5:80c4d829c3557135bab4adfa0691ef28	1.2 MiB	DFT calculations of CO adsorption on CeO2 (110) with PBE0 functional
PBE.zip MD5md5:eac0dfc336564aef5bb4c8a95719b968	4.2 MiB	DFT calculations of CO adsorption on CeO2 (111) and (110) with PBE functional
README.txt MD5md5:f1396ed67b28f8c1118abb6d224ce1c7	1.9 KiB	Description of the uploaded data

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External references

Keywords

Comparison between several functionals donation and backdonation effects DFT calculations and Infrared spectroscopy CeO2 (111) and (110)