CO interaction with Au atoms adsorbed on terrace, edge and corner sites of the MgO(1 0 0) surface. Electronic structure and vibrational analysis from DFT

Autores
Ferullo, Ricardo; Fuente, Silvia Andrea; Belelli, Patricia Gabriela; Castellani, Norberto Jorge
Año de publicación
2009
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The interaction of CO with Au atoms adsorbed on terrace and low-coordinates sites (edge and corner) of the MgO(1 0 0) surface was studied using the density functional theory (DFT) in combination with embedded cluster models. Surface anionic (O2-) and neutral oxygen vacancy (Fs) sites were considered. In all the cases, the CO stretching frequencies are shifted with respect to free CO with values between -232 and -358 cm-1. In particular, the values for Au on Fs at edge and corner are shifted to higher stretching frequencies by 100 and 59 cm-1, respectively, with respect to the value on a perfect MgO(1 0 0) surface. This result is in agreement with recent scanning tunneling microscopy and infrared spectroscopy experiments where a corresponding shift of 70 cm-1 was observed by comparing the measurements on perfect and O-deficient MgO(1 0 0) surfaces. However, these results are different than expected because Au atoms on Fs centers are negatively charged and, therefore, according to the generally accepted scheme the CO frequency should be red-shifted with respect to the adsorption on anionic five-coordinated site where the Au atom is essentially neutral. The following picture emerges from the present results: the single occupied HOMO(α) of Au atom on Fs at low-coordinated sites consists in two lobes extended sideward the Au atom. For symmetry reasons, this MO overlaps efficiently with the 2π* MO of CO. This bonding contribution to the Au-CO link is counteracted by a Pauli repulsion between the 5σ MO of CO and more internal orbitals (the HOMO-1(α) and the HOMO(β)) centered on Au. In consequence, CO is forced to vibrate against a region with a high electron density. This is the so-called "wall effect" which by itself contributes to higher CO frequency values. © 2009 Elsevier B.V. All rights reserved.
Fil: Ferullo, Ricardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina. Universidad Nacional del Sur. Departamento de Física; Argentina
Fil: Fuente, Silvia Andrea. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca; Argentina. Universidad Nacional del Sur. Departamento de Física; Argentina
Fil: Belelli, Patricia Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca; Argentina. Universidad Nacional del Sur. Departamento de Física; Argentina
Fil: Castellani, Norberto Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca; Argentina. Universidad Nacional del Sur. Departamento de Física; Argentina
Materia
Au/Mgo
Cluster Model
Co Adsorption
Dft
Model Catalysts
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:11336/66022
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/66022
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling CO interaction with Au atoms adsorbed on terrace, edge and corner sites of the MgO(1 0 0) surface. Electronic structure and vibrational analysis from DFTFerullo, RicardoFuente, Silvia AndreaBelelli, Patricia GabrielaCastellani, Norberto JorgeAu/MgoCluster ModelCo AdsorptionDftModel Catalystshttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1The interaction of CO with Au atoms adsorbed on terrace and low-coordinates sites (edge and corner) of the MgO(1 0 0) surface was studied using the density functional theory (DFT) in combination with embedded cluster models. Surface anionic (O2-) and neutral oxygen vacancy (Fs) sites were considered. In all the cases, the CO stretching frequencies are shifted with respect to free CO with values between -232 and -358 cm-1. In particular, the values for Au on Fs at edge and corner are shifted to higher stretching frequencies by 100 and 59 cm-1, respectively, with respect to the value on a perfect MgO(1 0 0) surface. This result is in agreement with recent scanning tunneling microscopy and infrared spectroscopy experiments where a corresponding shift of 70 cm-1 was observed by comparing the measurements on perfect and O-deficient MgO(1 0 0) surfaces. However, these results are different than expected because Au atoms on Fs centers are negatively charged and, therefore, according to the generally accepted scheme the CO frequency should be red-shifted with respect to the adsorption on anionic five-coordinated site where the Au atom is essentially neutral. The following picture emerges from the present results: the single occupied HOMO(α) of Au atom on Fs at low-coordinated sites consists in two lobes extended sideward the Au atom. For symmetry reasons, this MO overlaps efficiently with the 2π* MO of CO. This bonding contribution to the Au-CO link is counteracted by a Pauli repulsion between the 5σ MO of CO and more internal orbitals (the HOMO-1(α) and the HOMO(β)) centered on Au. In consequence, CO is forced to vibrate against a region with a high electron density. This is the so-called "wall effect" which by itself contributes to higher CO frequency values. © 2009 Elsevier B.V. All rights reserved.Fil: Ferullo, Ricardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina. Universidad Nacional del Sur. Departamento de Física; ArgentinaFil: Fuente, Silvia Andrea. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca; Argentina. Universidad Nacional del Sur. Departamento de Física; ArgentinaFil: Belelli, Patricia Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca; Argentina. Universidad Nacional del Sur. Departamento de Física; ArgentinaFil: Castellani, Norberto Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca; Argentina. Universidad Nacional del Sur. Departamento de Física; ArgentinaElsevier Science2009-05-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/66022Ferullo, Ricardo; Fuente, Silvia Andrea; Belelli, Patricia Gabriela; Castellani, Norberto Jorge; CO interaction with Au atoms adsorbed on terrace, edge and corner sites of the MgO(1 0 0) surface. Electronic structure and vibrational analysis from DFT; Elsevier Science; Surface Science; 603; 9; 1-5-2009; 1262-12690039-6028CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0039602809002465info:eu-repo/semantics/altIdentifier/doi/10.1016/j.susc.2009.03.015info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T15:44:46Zoai:ri.conicet.gov.ar:11336/66022instacron: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:34982025-10-15 15:44:47.182CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv CO interaction with Au atoms adsorbed on terrace, edge and corner sites of the MgO(1 0 0) surface. Electronic structure and vibrational analysis from DFT
title CO interaction with Au atoms adsorbed on terrace, edge and corner sites of the MgO(1 0 0) surface. Electronic structure and vibrational analysis from DFT
spellingShingle CO interaction with Au atoms adsorbed on terrace, edge and corner sites of the MgO(1 0 0) surface. Electronic structure and vibrational analysis from DFT
Ferullo, Ricardo
Au/Mgo
Cluster Model
Co Adsorption
Dft
Model Catalysts
title_short CO interaction with Au atoms adsorbed on terrace, edge and corner sites of the MgO(1 0 0) surface. Electronic structure and vibrational analysis from DFT
title_full CO interaction with Au atoms adsorbed on terrace, edge and corner sites of the MgO(1 0 0) surface. Electronic structure and vibrational analysis from DFT
title_fullStr CO interaction with Au atoms adsorbed on terrace, edge and corner sites of the MgO(1 0 0) surface. Electronic structure and vibrational analysis from DFT
title_full_unstemmed CO interaction with Au atoms adsorbed on terrace, edge and corner sites of the MgO(1 0 0) surface. Electronic structure and vibrational analysis from DFT
title_sort CO interaction with Au atoms adsorbed on terrace, edge and corner sites of the MgO(1 0 0) surface. Electronic structure and vibrational analysis from DFT
dc.creator.none.fl_str_mv Ferullo, Ricardo
Fuente, Silvia Andrea
Belelli, Patricia Gabriela
Castellani, Norberto Jorge
author Ferullo, Ricardo
author_facet Ferullo, Ricardo
Fuente, Silvia Andrea
Belelli, Patricia Gabriela
Castellani, Norberto Jorge
author_role author
author2 Fuente, Silvia Andrea
Belelli, Patricia Gabriela
Castellani, Norberto Jorge
author2_role author
author
author
dc.subject.none.fl_str_mv Au/Mgo
Cluster Model
Co Adsorption
Dft
Model Catalysts
topic Au/Mgo
Cluster Model
Co Adsorption
Dft
Model Catalysts
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The interaction of CO with Au atoms adsorbed on terrace and low-coordinates sites (edge and corner) of the MgO(1 0 0) surface was studied using the density functional theory (DFT) in combination with embedded cluster models. Surface anionic (O2-) and neutral oxygen vacancy (Fs) sites were considered. In all the cases, the CO stretching frequencies are shifted with respect to free CO with values between -232 and -358 cm-1. In particular, the values for Au on Fs at edge and corner are shifted to higher stretching frequencies by 100 and 59 cm-1, respectively, with respect to the value on a perfect MgO(1 0 0) surface. This result is in agreement with recent scanning tunneling microscopy and infrared spectroscopy experiments where a corresponding shift of 70 cm-1 was observed by comparing the measurements on perfect and O-deficient MgO(1 0 0) surfaces. However, these results are different than expected because Au atoms on Fs centers are negatively charged and, therefore, according to the generally accepted scheme the CO frequency should be red-shifted with respect to the adsorption on anionic five-coordinated site where the Au atom is essentially neutral. The following picture emerges from the present results: the single occupied HOMO(α) of Au atom on Fs at low-coordinated sites consists in two lobes extended sideward the Au atom. For symmetry reasons, this MO overlaps efficiently with the 2π* MO of CO. This bonding contribution to the Au-CO link is counteracted by a Pauli repulsion between the 5σ MO of CO and more internal orbitals (the HOMO-1(α) and the HOMO(β)) centered on Au. In consequence, CO is forced to vibrate against a region with a high electron density. This is the so-called "wall effect" which by itself contributes to higher CO frequency values. © 2009 Elsevier B.V. All rights reserved.
Fil: Ferullo, Ricardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina. Universidad Nacional del Sur. Departamento de Física; Argentina
Fil: Fuente, Silvia Andrea. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca; Argentina. Universidad Nacional del Sur. Departamento de Física; Argentina
Fil: Belelli, Patricia Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca; Argentina. Universidad Nacional del Sur. Departamento de Física; Argentina
Fil: Castellani, Norberto Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca; Argentina. Universidad Nacional del Sur. Departamento de Física; Argentina
description The interaction of CO with Au atoms adsorbed on terrace and low-coordinates sites (edge and corner) of the MgO(1 0 0) surface was studied using the density functional theory (DFT) in combination with embedded cluster models. Surface anionic (O2-) and neutral oxygen vacancy (Fs) sites were considered. In all the cases, the CO stretching frequencies are shifted with respect to free CO with values between -232 and -358 cm-1. In particular, the values for Au on Fs at edge and corner are shifted to higher stretching frequencies by 100 and 59 cm-1, respectively, with respect to the value on a perfect MgO(1 0 0) surface. This result is in agreement with recent scanning tunneling microscopy and infrared spectroscopy experiments where a corresponding shift of 70 cm-1 was observed by comparing the measurements on perfect and O-deficient MgO(1 0 0) surfaces. However, these results are different than expected because Au atoms on Fs centers are negatively charged and, therefore, according to the generally accepted scheme the CO frequency should be red-shifted with respect to the adsorption on anionic five-coordinated site where the Au atom is essentially neutral. The following picture emerges from the present results: the single occupied HOMO(α) of Au atom on Fs at low-coordinated sites consists in two lobes extended sideward the Au atom. For symmetry reasons, this MO overlaps efficiently with the 2π* MO of CO. This bonding contribution to the Au-CO link is counteracted by a Pauli repulsion between the 5σ MO of CO and more internal orbitals (the HOMO-1(α) and the HOMO(β)) centered on Au. In consequence, CO is forced to vibrate against a region with a high electron density. This is the so-called "wall effect" which by itself contributes to higher CO frequency values. © 2009 Elsevier B.V. All rights reserved.
publishDate 2009
dc.date.none.fl_str_mv 2009-05-01
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/11336/66022
Ferullo, Ricardo; Fuente, Silvia Andrea; Belelli, Patricia Gabriela; Castellani, Norberto Jorge; CO interaction with Au atoms adsorbed on terrace, edge and corner sites of the MgO(1 0 0) surface. Electronic structure and vibrational analysis from DFT; Elsevier Science; Surface Science; 603; 9; 1-5-2009; 1262-1269
0039-6028
CONICET Digital
CONICET
url http://hdl.handle.net/11336/66022
identifier_str_mv Ferullo, Ricardo; Fuente, Silvia Andrea; Belelli, Patricia Gabriela; Castellani, Norberto Jorge; CO interaction with Au atoms adsorbed on terrace, edge and corner sites of the MgO(1 0 0) surface. Electronic structure and vibrational analysis from DFT; Elsevier Science; Surface Science; 603; 9; 1-5-2009; 1262-1269
0039-6028
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0039602809002465
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.susc.2009.03.015
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
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier Science
publisher.none.fl_str_mv Elsevier Science
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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