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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/66022
Ver los metadatos del registro completo
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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 Técnicas2025-09-29T10:46:14Zoai: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:34982025-09-29 10:46:15.071CONICET 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) |
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CONICET Digital (CONICET) |
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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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13.070432 |