Facet-dependent stability of near-surface oxygen vacancies and excess charge localization at CeO2surfaces

Autores
Pérez Bailac, Patricia; Lustemberg, Pablo German; Ganduglia Pirovano, M. Verónica
Año de publicación
2021
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
To study the dependence of the relative stability of surface (V A) and subsurface (VB) oxygen vacancies with the crystal facet of CeO2, the reduced (100), (110) and (111) surfaces, with two different concentrations of vacancies, were investigated by means of density functional theory (DFT + U) calculations. The results show that the trend in the near-surface vacancy formation energies for comparable vacancy spacings, i.e. (110) < (100) < (111), does not follow the one in the surface stability of the facets, i.e. (111) < (110) < (100). The results also reveal that the preference of vacancies for surface or subsurface sites, as well as the preferred location of the associated Ce3+ polarons, are facet- and concentration-dependent. At the higher vacancy concentration, the V A is more stable than the V B at the (110) facet whereas at the (111), it is the other way around, and at the (100) facet, both the V A and the VB have similar stability. The stability of the V A vacancies, compared to that of the V B, is accentuated as the concentration decreases. Nearest neighbor polarons to the vacant sites are only observed for the less densely packed (110) and (100) facets. These findings are rationalized in terms of the packing density of the facets, the lattice relaxation effects induced by vacancy formation and the localization of the excess charge, as well as the repulsive Ce3+-Ce3+ interactions.
Fil: Pérez Bailac, Patricia. Universidad Autónoma de Madrid; España. Consejo Superior de Investigaciones Científicas; España
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: Ganduglia Pirovano, M. Verónica. Consejo Superior de Investigaciones Científicas; España
Materia
CERIUM OXIDE SURFACES
EXCESS CHARGE LOCALIZATION
FACET-DEPENDENT STABILITY
LATTICE RELAXATION
OXYGEN VACANCIES
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:11336/182272
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/182272
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Facet-dependent stability of near-surface oxygen vacancies and excess charge localization at CeO2surfacesPérez Bailac, PatriciaLustemberg, Pablo GermanGanduglia Pirovano, M. VerónicaCERIUM OXIDE SURFACESEXCESS CHARGE LOCALIZATIONFACET-DEPENDENT STABILITYLATTICE RELAXATIONOXYGEN VACANCIEShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1To study the dependence of the relative stability of surface (V A) and subsurface (VB) oxygen vacancies with the crystal facet of CeO2, the reduced (100), (110) and (111) surfaces, with two different concentrations of vacancies, were investigated by means of density functional theory (DFT + U) calculations. The results show that the trend in the near-surface vacancy formation energies for comparable vacancy spacings, i.e. (110) < (100) < (111), does not follow the one in the surface stability of the facets, i.e. (111) < (110) < (100). The results also reveal that the preference of vacancies for surface or subsurface sites, as well as the preferred location of the associated Ce3+ polarons, are facet- and concentration-dependent. At the higher vacancy concentration, the V A is more stable than the V B at the (110) facet whereas at the (111), it is the other way around, and at the (100) facet, both the V A and the VB have similar stability. The stability of the V A vacancies, compared to that of the V B, is accentuated as the concentration decreases. Nearest neighbor polarons to the vacant sites are only observed for the less densely packed (110) and (100) facets. These findings are rationalized in terms of the packing density of the facets, the lattice relaxation effects induced by vacancy formation and the localization of the excess charge, as well as the repulsive Ce3+-Ce3+ interactions.Fil: Pérez Bailac, Patricia. Universidad Autónoma de Madrid; España. Consejo Superior de Investigaciones Científicas; EspañaFil: 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: Ganduglia Pirovano, M. Verónica. Consejo Superior de Investigaciones Científicas; EspañaIOP Publishing2021-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/182272Pérez Bailac, Patricia; Lustemberg, Pablo German; Ganduglia Pirovano, M. Verónica; Facet-dependent stability of near-surface oxygen vacancies and excess charge localization at CeO2surfaces; IOP Publishing; Journal of Physics: Condensed Matter; 33; 50; 12-2021; 1-150953-8984CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1088/1361-648X/ac238binfo:eu-repo/semantics/altIdentifier/url/https://iopscience.iop.org/article/10.1088/1361-648X/ac238binfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:13:53Zoai:ri.conicet.gov.ar:11336/182272instacron: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:34982025-09-10 13:13:53.991CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Facet-dependent stability of near-surface oxygen vacancies and excess charge localization at CeO2surfaces
title Facet-dependent stability of near-surface oxygen vacancies and excess charge localization at CeO2surfaces
spellingShingle Facet-dependent stability of near-surface oxygen vacancies and excess charge localization at CeO2surfaces
Pérez Bailac, Patricia
CERIUM OXIDE SURFACES
EXCESS CHARGE LOCALIZATION
FACET-DEPENDENT STABILITY
LATTICE RELAXATION
OXYGEN VACANCIES
title_short Facet-dependent stability of near-surface oxygen vacancies and excess charge localization at CeO2surfaces
title_full Facet-dependent stability of near-surface oxygen vacancies and excess charge localization at CeO2surfaces
title_fullStr Facet-dependent stability of near-surface oxygen vacancies and excess charge localization at CeO2surfaces
title_full_unstemmed Facet-dependent stability of near-surface oxygen vacancies and excess charge localization at CeO2surfaces
title_sort Facet-dependent stability of near-surface oxygen vacancies and excess charge localization at CeO2surfaces
dc.creator.none.fl_str_mv Pérez Bailac, Patricia
Lustemberg, Pablo German
Ganduglia Pirovano, M. Verónica
author Pérez Bailac, Patricia
author_facet Pérez Bailac, Patricia
Lustemberg, Pablo German
Ganduglia Pirovano, M. Verónica
author_role author
author2 Lustemberg, Pablo German
Ganduglia Pirovano, M. Verónica
author2_role author
author
dc.subject.none.fl_str_mv CERIUM OXIDE SURFACES
EXCESS CHARGE LOCALIZATION
FACET-DEPENDENT STABILITY
LATTICE RELAXATION
OXYGEN VACANCIES
topic CERIUM OXIDE SURFACES
EXCESS CHARGE LOCALIZATION
FACET-DEPENDENT STABILITY
LATTICE RELAXATION
OXYGEN VACANCIES
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv To study the dependence of the relative stability of surface (V A) and subsurface (VB) oxygen vacancies with the crystal facet of CeO2, the reduced (100), (110) and (111) surfaces, with two different concentrations of vacancies, were investigated by means of density functional theory (DFT + U) calculations. The results show that the trend in the near-surface vacancy formation energies for comparable vacancy spacings, i.e. (110) < (100) < (111), does not follow the one in the surface stability of the facets, i.e. (111) < (110) < (100). The results also reveal that the preference of vacancies for surface or subsurface sites, as well as the preferred location of the associated Ce3+ polarons, are facet- and concentration-dependent. At the higher vacancy concentration, the V A is more stable than the V B at the (110) facet whereas at the (111), it is the other way around, and at the (100) facet, both the V A and the VB have similar stability. The stability of the V A vacancies, compared to that of the V B, is accentuated as the concentration decreases. Nearest neighbor polarons to the vacant sites are only observed for the less densely packed (110) and (100) facets. These findings are rationalized in terms of the packing density of the facets, the lattice relaxation effects induced by vacancy formation and the localization of the excess charge, as well as the repulsive Ce3+-Ce3+ interactions.
Fil: Pérez Bailac, Patricia. Universidad Autónoma de Madrid; España. Consejo Superior de Investigaciones Científicas; España
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: Ganduglia Pirovano, M. Verónica. Consejo Superior de Investigaciones Científicas; España
description To study the dependence of the relative stability of surface (V A) and subsurface (VB) oxygen vacancies with the crystal facet of CeO2, the reduced (100), (110) and (111) surfaces, with two different concentrations of vacancies, were investigated by means of density functional theory (DFT + U) calculations. The results show that the trend in the near-surface vacancy formation energies for comparable vacancy spacings, i.e. (110) < (100) < (111), does not follow the one in the surface stability of the facets, i.e. (111) < (110) < (100). The results also reveal that the preference of vacancies for surface or subsurface sites, as well as the preferred location of the associated Ce3+ polarons, are facet- and concentration-dependent. At the higher vacancy concentration, the V A is more stable than the V B at the (110) facet whereas at the (111), it is the other way around, and at the (100) facet, both the V A and the VB have similar stability. The stability of the V A vacancies, compared to that of the V B, is accentuated as the concentration decreases. Nearest neighbor polarons to the vacant sites are only observed for the less densely packed (110) and (100) facets. These findings are rationalized in terms of the packing density of the facets, the lattice relaxation effects induced by vacancy formation and the localization of the excess charge, as well as the repulsive Ce3+-Ce3+ interactions.
publishDate 2021
dc.date.none.fl_str_mv 2021-12
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/11336/182272
Pérez Bailac, Patricia; Lustemberg, Pablo German; Ganduglia Pirovano, M. Verónica; Facet-dependent stability of near-surface oxygen vacancies and excess charge localization at CeO2surfaces; IOP Publishing; Journal of Physics: Condensed Matter; 33; 50; 12-2021; 1-15
0953-8984
CONICET Digital
CONICET
url http://hdl.handle.net/11336/182272
identifier_str_mv Pérez Bailac, Patricia; Lustemberg, Pablo German; Ganduglia Pirovano, M. Verónica; Facet-dependent stability of near-surface oxygen vacancies and excess charge localization at CeO2surfaces; IOP Publishing; Journal of Physics: Condensed Matter; 33; 50; 12-2021; 1-15
0953-8984
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1088/1361-648X/ac238b
info:eu-repo/semantics/altIdentifier/url/https://iopscience.iop.org/article/10.1088/1361-648X/ac238b
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
dc.publisher.none.fl_str_mv IOP Publishing
publisher.none.fl_str_mv IOP Publishing
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 12.993085

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