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

Autores
Lustemberg, Pablo German; Plessow, Philipp N.; Wang, Yuemin; Yang, Chengwu; Nefedov, Alexei; Studt, Felix; Wöll, Christof; Ganduglia Pirovano, Maria Veronica
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
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 density-functional theory (DFT) is explained in terms of its inability to accurately describe the facet- A nd configuration-specific donation and backdonation effects that control the changes in the Câ"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.
Fil: Lustemberg, Pablo German. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Física de Rosario. Universidad Nacional de Rosario. Instituto de Física de Rosario; Argentina. Consejo Superior de Investigaciones Científicas; España
Fil: Plessow, Philipp N.. Karlsruher Institut fur Technologie; Alemania
Fil: Wang, Yuemin. Karlsruher Institut fur Technologie; Alemania
Fil: Yang, Chengwu. Karlsruher Institut fur Technologie; Alemania
Fil: Nefedov, Alexei. Karlsruher Institut fur Technologie; Alemania
Fil: Studt, Felix. Karlsruher Institut fur Technologie; Alemania
Fil: Wöll, Christof. Karlsruher Institut fur Technologie; Alemania
Fil: Ganduglia Pirovano, Maria Veronica. Karlsruher Institut fur Technologie; Alemania
Materia
CO frequency shift
PBE+U
Hybrid calculation
IRRAS spectra
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/144120
Acceder
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network_acronym_str CONICETDig
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network_name_str CONICET Digital (CONICET)
spelling Vibrational Frequencies of Cerium-Oxide-Bound CO: A Challenge for Conventional DFT MethodsLustemberg, Pablo GermanPlessow, Philipp N.Wang, YueminYang, ChengwuNefedov, AlexeiStudt, FelixWöll, ChristofGanduglia Pirovano, Maria VeronicaCO frequency shiftPBE+UHybrid calculationIRRAS spectrahttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1In 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 density-functional theory (DFT) is explained in terms of its inability to accurately describe the facet- A nd configuration-specific donation and backdonation effects that control the changes in the Câ"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.Fil: Lustemberg, Pablo German. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Física de Rosario. Universidad Nacional de Rosario. Instituto de Física de Rosario; Argentina. Consejo Superior de Investigaciones Científicas; EspañaFil: Plessow, Philipp N.. Karlsruher Institut fur Technologie; AlemaniaFil: Wang, Yuemin. Karlsruher Institut fur Technologie; AlemaniaFil: Yang, Chengwu. Karlsruher Institut fur Technologie; AlemaniaFil: Nefedov, Alexei. Karlsruher Institut fur Technologie; AlemaniaFil: Studt, Felix. Karlsruher Institut fur Technologie; AlemaniaFil: Wöll, Christof. Karlsruher Institut fur Technologie; AlemaniaFil: Ganduglia Pirovano, Maria Veronica. Karlsruher Institut fur Technologie; AlemaniaAmerican Physical Society2020-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/144120Lustemberg, Pablo German; Plessow, Philipp N.; Wang, Yuemin; Yang, Chengwu; Nefedov, Alexei; et al.; Vibrational Frequencies of Cerium-Oxide-Bound CO: A Challenge for Conventional DFT Methods; American Physical Society; Physical Review Letters; 125; 25; 12-2020; 1-70031-9007CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1103/PhysRevLett.125.256101info:eu-repo/semantics/altIdentifier/url/https://journals.aps.org/prl/abstract/10.1103/PhysRevLett.125.256101info:eu-repo/semantics/altIdentifier/url/https://arxiv.org/abs/2011.06419info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:03:35Zoai:ri.conicet.gov.ar:11336/144120instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:03:35.471CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Vibrational Frequencies of Cerium-Oxide-Bound CO: A Challenge for Conventional DFT Methods
title Vibrational Frequencies of Cerium-Oxide-Bound CO: A Challenge for Conventional DFT Methods
spellingShingle Vibrational Frequencies of Cerium-Oxide-Bound CO: A Challenge for Conventional DFT Methods
Lustemberg, Pablo German
CO frequency shift
PBE+U
Hybrid calculation
IRRAS spectra
title_short Vibrational Frequencies of Cerium-Oxide-Bound CO: A Challenge for Conventional DFT Methods
title_full Vibrational Frequencies of Cerium-Oxide-Bound CO: A Challenge for Conventional DFT Methods
title_fullStr Vibrational Frequencies of Cerium-Oxide-Bound CO: A Challenge for Conventional DFT Methods
title_full_unstemmed Vibrational Frequencies of Cerium-Oxide-Bound CO: A Challenge for Conventional DFT Methods
title_sort Vibrational Frequencies of Cerium-Oxide-Bound CO: A Challenge for Conventional DFT Methods
dc.creator.none.fl_str_mv Lustemberg, Pablo German
Plessow, Philipp N.
Wang, Yuemin
Yang, Chengwu
Nefedov, Alexei
Studt, Felix
Wöll, Christof
Ganduglia Pirovano, Maria Veronica
author Lustemberg, Pablo German
author_facet Lustemberg, Pablo German
Plessow, Philipp N.
Wang, Yuemin
Yang, Chengwu
Nefedov, Alexei
Studt, Felix
Wöll, Christof
Ganduglia Pirovano, Maria Veronica
author_role author
author2 Plessow, Philipp N.
Wang, Yuemin
Yang, Chengwu
Nefedov, Alexei
Studt, Felix
Wöll, Christof
Ganduglia Pirovano, Maria Veronica
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv CO frequency shift
PBE+U
Hybrid calculation
IRRAS spectra
topic CO frequency shift
PBE+U
Hybrid calculation
IRRAS spectra
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv 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 density-functional theory (DFT) is explained in terms of its inability to accurately describe the facet- A nd configuration-specific donation and backdonation effects that control the changes in the Câ"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.
Fil: Lustemberg, Pablo German. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Física de Rosario. Universidad Nacional de Rosario. Instituto de Física de Rosario; Argentina. Consejo Superior de Investigaciones Científicas; España
Fil: Plessow, Philipp N.. Karlsruher Institut fur Technologie; Alemania
Fil: Wang, Yuemin. Karlsruher Institut fur Technologie; Alemania
Fil: Yang, Chengwu. Karlsruher Institut fur Technologie; Alemania
Fil: Nefedov, Alexei. Karlsruher Institut fur Technologie; Alemania
Fil: Studt, Felix. Karlsruher Institut fur Technologie; Alemania
Fil: Wöll, Christof. Karlsruher Institut fur Technologie; Alemania
Fil: Ganduglia Pirovano, Maria Veronica. Karlsruher Institut fur Technologie; Alemania
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 density-functional theory (DFT) is explained in terms of its inability to accurately describe the facet- A nd configuration-specific donation and backdonation effects that control the changes in the Câ"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.
publishDate 2020
dc.date.none.fl_str_mv 2020-12
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/144120
Lustemberg, Pablo German; Plessow, Philipp N.; Wang, Yuemin; Yang, Chengwu; Nefedov, Alexei; et al.; Vibrational Frequencies of Cerium-Oxide-Bound CO: A Challenge for Conventional DFT Methods; American Physical Society; Physical Review Letters; 125; 25; 12-2020; 1-7
0031-9007
CONICET Digital
CONICET
url http://hdl.handle.net/11336/144120
identifier_str_mv Lustemberg, Pablo German; Plessow, Philipp N.; Wang, Yuemin; Yang, Chengwu; Nefedov, Alexei; et al.; Vibrational Frequencies of Cerium-Oxide-Bound CO: A Challenge for Conventional DFT Methods; American Physical Society; Physical Review Letters; 125; 25; 12-2020; 1-7
0031-9007
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1103/PhysRevLett.125.256101
info:eu-repo/semantics/altIdentifier/url/https://journals.aps.org/prl/abstract/10.1103/PhysRevLett.125.256101
info:eu-repo/semantics/altIdentifier/url/https://arxiv.org/abs/2011.06419
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Physical Society
publisher.none.fl_str_mv American Physical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.070432

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