CO adsorption on CeO2(111): A CCSD(T) benchmark study using an embedded-cluster model.
| Autor: | Vázquez Quesada J; Institut für Nanotechnologie, Karlsruher Institut für Technologie (KIT), Kaiserstraße 12, 76131 Karlsruhe, Germany., Bernart S; Institut für Katalyseforschung und Technologie, Karlsruhe Institut für Technologie (KIT), Kaiserstraße 12, 76131 Karlsruhe, Germany., Studt F; Institut für Katalyseforschung und Technologie, Karlsruhe Institut für Technologie (KIT), Kaiserstraße 12, 76131 Karlsruhe, Germany., Wang Y; Institut für Funktionelle Grenzflächen, Karlsruher Institut für Technologie (KIT), Kaiserstraße 12, 76131 Karlsruhe, Germany., Fink K; Institut für Nanotechnologie, Karlsruher Institut für Technologie (KIT), Kaiserstraße 12, 76131 Karlsruhe, Germany. |
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| Jazyk: | angličtina |
| Zdroj: | The Journal of chemical physics [J Chem Phys] 2024 Dec 14; Vol. 161 (22). |
| DOI: | 10.1063/5.0231189 |
| Abstrakt: | A benchmark model that combines an embedded-cluster approach for ionic surfaces with wavefunction-based methods to predict the vibrational frequencies of molecules adsorbed on surfaces is presented. As a representative case, the adsorption of CO on the lowest index non-polar and most stable facet of CeO2, that is, (111) was studied. The CO harmonic vibrational frequencies were not scaled semiempirically but explicitly corrected for anharmonic effects, which amount to about 25 cm-1 with all tested methods. The second-order Møller-Plesset perturbation method (MP2) tends to underestimate the CO harmonic frequency by about 40-45 cm-1 in comparison with the results obtained with the coupled-cluster singles and doubles with perturbational treatment of triple excitation method [CCSD(T)] and independently from the basis set used. The best estimate for the CO vibrational frequency (low-coverage case) differs by 12 cm-1 with the experimental value obtained by infrared reflexion absorption spectroscopy of 1 monolayer CO adsorbed on the oxidized CeO2(111) surface. In addition, a conservative estimate of the adsorption energy of about -0.22 ± -0.07 eV obtained at the CCSD(T) level confirms the physisorption character of the adsorption of CO on the CeO2(111) surface. (© 2024 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).) |
| Databáze: | MEDLINE |
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