Mechanistic framework for the formation of different sulfur species by electron irradiation of n -Dodecanethiol Self-Assembled monolayers on Au(111) and Au(100)

Autores
Aagaard, Natalia Desiré; Azcárate, Julio César; Olmos Asar, Jimena Anahí; Mariscal, Marcelo; Solla-Gullón, José; Zelaya, Maria Eugenia; Fonticelli, Mariano Hernan
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The electron-induced damage in self-assembled monolayers (SAMs) of n-dodecanethiolate on Au(111) and Au(100) single-crystalline surfaces is investigated in situ by X-ray photoelectron spectroscopy. The same irradiation dose produced different adsorbed groups. The damage at the headgroup-substrate interface leads to find dialkyl sulfide (RS-R′) on Au(111), while dialkyl disulfide (RS-SR) and/or thiol (RSH) were produced on Au(100). With regard to C species, significant amounts of CC are generated on Au(111) but not on Au(100), showing that double bond formation is not triggered through the same pathways on these surfaces. Detailed analysis of a variety of mechanisms, which involved cationic (RS+), anionic (RS-), or thiyl radical (RS•) species, in combination with ab initio density functional theory (DFT) calculation, leads to the conclusion that the radical pathways successfully explain the experimental results. Molecular dynamics simulations show that the n-dodecanethiolate SAMs on both surfaces are equivalent with regard to the van der Waals interactions. The breakage of the S-Au bonds is studied by means of DFT calculations. The thiyl radical would form close to the Au(100) surface, making it likely to react with another thiyl radical or thiolate to form the RS-SR species. On the other hand, for Au(111), the thiyl radical would form farther from the surface, reacting with the alkyl chains of neighboring molecules to form RS-R′ species. The mechanistic framework proposed here is very useful to explain the behavior of related systems.
Fil: Aagaard, Natalia Desiré. Comision Nacional de Energia Atomica. Gerencia de Area de Investigaciones y Aplicaciones No Nucleares (cac).; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Azcárate, Julio César. Comision Nacional de Energia Atomica. Gerencia de Area de Investigaciones y Aplicaciones No Nucleares (cac).; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Olmos Asar, Jimena Anahí. Universidad Nacional de Córdoba. Facultad de Cs.químicas. Departamento de Química Teórica y Computacional; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Mariscal, Marcelo. Universidad Nacional de Córdoba. Facultad de Cs.químicas. Departamento de Química Teórica y Computacional; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Solla-Gullón, José. Universidad de Alicante; España
Fil: Zelaya, Maria Eugenia. Comision Nacional de Energia Atomica. Gerencia de Area de Investigaciones y Aplicaciones No Nucleares (cac).; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Fonticelli, Mariano Hernan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Materia
Thiols
Gold
SAMs
XPS
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:11336/144374
Acceder
id CONICETDig_a0ed2ad8c9d8153d8e3742023a5bf2e4
oai_identifier_str oai:ri.conicet.gov.ar:11336/144374
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Mechanistic framework for the formation of different sulfur species by electron irradiation of n -Dodecanethiol Self-Assembled monolayers on Au(111) and Au(100)Aagaard, Natalia DesiréAzcárate, Julio CésarOlmos Asar, Jimena AnahíMariscal, MarceloSolla-Gullón, JoséZelaya, Maria EugeniaFonticelli, Mariano HernanThiolsGoldSAMsXPShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The electron-induced damage in self-assembled monolayers (SAMs) of n-dodecanethiolate on Au(111) and Au(100) single-crystalline surfaces is investigated in situ by X-ray photoelectron spectroscopy. The same irradiation dose produced different adsorbed groups. The damage at the headgroup-substrate interface leads to find dialkyl sulfide (RS-R′) on Au(111), while dialkyl disulfide (RS-SR) and/or thiol (RSH) were produced on Au(100). With regard to C species, significant amounts of CC are generated on Au(111) but not on Au(100), showing that double bond formation is not triggered through the same pathways on these surfaces. Detailed analysis of a variety of mechanisms, which involved cationic (RS+), anionic (RS-), or thiyl radical (RS•) species, in combination with ab initio density functional theory (DFT) calculation, leads to the conclusion that the radical pathways successfully explain the experimental results. Molecular dynamics simulations show that the n-dodecanethiolate SAMs on both surfaces are equivalent with regard to the van der Waals interactions. The breakage of the S-Au bonds is studied by means of DFT calculations. The thiyl radical would form close to the Au(100) surface, making it likely to react with another thiyl radical or thiolate to form the RS-SR species. On the other hand, for Au(111), the thiyl radical would form farther from the surface, reacting with the alkyl chains of neighboring molecules to form RS-R′ species. The mechanistic framework proposed here is very useful to explain the behavior of related systems.Fil: Aagaard, Natalia Desiré. Comision Nacional de Energia Atomica. Gerencia de Area de Investigaciones y Aplicaciones No Nucleares (cac).; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Azcárate, Julio César. Comision Nacional de Energia Atomica. Gerencia de Area de Investigaciones y Aplicaciones No Nucleares (cac).; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Olmos Asar, Jimena Anahí. Universidad Nacional de Córdoba. Facultad de Cs.químicas. Departamento de Química Teórica y Computacional; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Mariscal, Marcelo. Universidad Nacional de Córdoba. Facultad de Cs.químicas. Departamento de Química Teórica y Computacional; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Solla-Gullón, José. Universidad de Alicante; EspañaFil: Zelaya, Maria Eugenia. Comision Nacional de Energia Atomica. Gerencia de Area de Investigaciones y Aplicaciones No Nucleares (cac).; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Fonticelli, Mariano Hernan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaAmerican Chemical Society2020-10info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/144374Aagaard, Natalia Desiré; Azcárate, Julio César; Olmos Asar, Jimena Anahí; Mariscal, Marcelo; Solla-Gullón, José; et al.; Mechanistic framework for the formation of different sulfur species by electron irradiation of n -Dodecanethiol Self-Assembled monolayers on Au(111) and Au(100); American Chemical Society; Journal of Physical Chemistry C; 124; 41; 10-2020; 22591-226001932-74471932-7455CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpcc.0c07106info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.0c07106info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:42:53Zoai:ri.conicet.gov.ar:11336/144374instacron: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 09:42:53.43CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Mechanistic framework for the formation of different sulfur species by electron irradiation of n -Dodecanethiol Self-Assembled monolayers on Au(111) and Au(100)
title Mechanistic framework for the formation of different sulfur species by electron irradiation of n -Dodecanethiol Self-Assembled monolayers on Au(111) and Au(100)
spellingShingle Mechanistic framework for the formation of different sulfur species by electron irradiation of n -Dodecanethiol Self-Assembled monolayers on Au(111) and Au(100)
Aagaard, Natalia Desiré
Thiols
Gold
SAMs
XPS
title_short Mechanistic framework for the formation of different sulfur species by electron irradiation of n -Dodecanethiol Self-Assembled monolayers on Au(111) and Au(100)
title_full Mechanistic framework for the formation of different sulfur species by electron irradiation of n -Dodecanethiol Self-Assembled monolayers on Au(111) and Au(100)
title_fullStr Mechanistic framework for the formation of different sulfur species by electron irradiation of n -Dodecanethiol Self-Assembled monolayers on Au(111) and Au(100)
title_full_unstemmed Mechanistic framework for the formation of different sulfur species by electron irradiation of n -Dodecanethiol Self-Assembled monolayers on Au(111) and Au(100)
title_sort Mechanistic framework for the formation of different sulfur species by electron irradiation of n -Dodecanethiol Self-Assembled monolayers on Au(111) and Au(100)
dc.creator.none.fl_str_mv Aagaard, Natalia Desiré
Azcárate, Julio César
Olmos Asar, Jimena Anahí
Mariscal, Marcelo
Solla-Gullón, José
Zelaya, Maria Eugenia
Fonticelli, Mariano Hernan
author Aagaard, Natalia Desiré
author_facet Aagaard, Natalia Desiré
Azcárate, Julio César
Olmos Asar, Jimena Anahí
Mariscal, Marcelo
Solla-Gullón, José
Zelaya, Maria Eugenia
Fonticelli, Mariano Hernan
author_role author
author2 Azcárate, Julio César
Olmos Asar, Jimena Anahí
Mariscal, Marcelo
Solla-Gullón, José
Zelaya, Maria Eugenia
Fonticelli, Mariano Hernan
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Thiols
Gold
SAMs
XPS
topic Thiols
Gold
SAMs
XPS
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The electron-induced damage in self-assembled monolayers (SAMs) of n-dodecanethiolate on Au(111) and Au(100) single-crystalline surfaces is investigated in situ by X-ray photoelectron spectroscopy. The same irradiation dose produced different adsorbed groups. The damage at the headgroup-substrate interface leads to find dialkyl sulfide (RS-R′) on Au(111), while dialkyl disulfide (RS-SR) and/or thiol (RSH) were produced on Au(100). With regard to C species, significant amounts of CC are generated on Au(111) but not on Au(100), showing that double bond formation is not triggered through the same pathways on these surfaces. Detailed analysis of a variety of mechanisms, which involved cationic (RS+), anionic (RS-), or thiyl radical (RS•) species, in combination with ab initio density functional theory (DFT) calculation, leads to the conclusion that the radical pathways successfully explain the experimental results. Molecular dynamics simulations show that the n-dodecanethiolate SAMs on both surfaces are equivalent with regard to the van der Waals interactions. The breakage of the S-Au bonds is studied by means of DFT calculations. The thiyl radical would form close to the Au(100) surface, making it likely to react with another thiyl radical or thiolate to form the RS-SR species. On the other hand, for Au(111), the thiyl radical would form farther from the surface, reacting with the alkyl chains of neighboring molecules to form RS-R′ species. The mechanistic framework proposed here is very useful to explain the behavior of related systems.
Fil: Aagaard, Natalia Desiré. Comision Nacional de Energia Atomica. Gerencia de Area de Investigaciones y Aplicaciones No Nucleares (cac).; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Azcárate, Julio César. Comision Nacional de Energia Atomica. Gerencia de Area de Investigaciones y Aplicaciones No Nucleares (cac).; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Olmos Asar, Jimena Anahí. Universidad Nacional de Córdoba. Facultad de Cs.químicas. Departamento de Química Teórica y Computacional; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Mariscal, Marcelo. Universidad Nacional de Córdoba. Facultad de Cs.químicas. Departamento de Química Teórica y Computacional; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Solla-Gullón, José. Universidad de Alicante; España
Fil: Zelaya, Maria Eugenia. Comision Nacional de Energia Atomica. Gerencia de Area de Investigaciones y Aplicaciones No Nucleares (cac).; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Fonticelli, Mariano Hernan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
description The electron-induced damage in self-assembled monolayers (SAMs) of n-dodecanethiolate on Au(111) and Au(100) single-crystalline surfaces is investigated in situ by X-ray photoelectron spectroscopy. The same irradiation dose produced different adsorbed groups. The damage at the headgroup-substrate interface leads to find dialkyl sulfide (RS-R′) on Au(111), while dialkyl disulfide (RS-SR) and/or thiol (RSH) were produced on Au(100). With regard to C species, significant amounts of CC are generated on Au(111) but not on Au(100), showing that double bond formation is not triggered through the same pathways on these surfaces. Detailed analysis of a variety of mechanisms, which involved cationic (RS+), anionic (RS-), or thiyl radical (RS•) species, in combination with ab initio density functional theory (DFT) calculation, leads to the conclusion that the radical pathways successfully explain the experimental results. Molecular dynamics simulations show that the n-dodecanethiolate SAMs on both surfaces are equivalent with regard to the van der Waals interactions. The breakage of the S-Au bonds is studied by means of DFT calculations. The thiyl radical would form close to the Au(100) surface, making it likely to react with another thiyl radical or thiolate to form the RS-SR species. On the other hand, for Au(111), the thiyl radical would form farther from the surface, reacting with the alkyl chains of neighboring molecules to form RS-R′ species. The mechanistic framework proposed here is very useful to explain the behavior of related systems.
publishDate 2020
dc.date.none.fl_str_mv 2020-10
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/11336/144374
Aagaard, Natalia Desiré; Azcárate, Julio César; Olmos Asar, Jimena Anahí; Mariscal, Marcelo; Solla-Gullón, José; et al.; Mechanistic framework for the formation of different sulfur species by electron irradiation of n -Dodecanethiol Self-Assembled monolayers on Au(111) and Au(100); American Chemical Society; Journal of Physical Chemistry C; 124; 41; 10-2020; 22591-22600
1932-7447
1932-7455
CONICET Digital
CONICET
url http://hdl.handle.net/11336/144374
identifier_str_mv Aagaard, Natalia Desiré; Azcárate, Julio César; Olmos Asar, Jimena Anahí; Mariscal, Marcelo; Solla-Gullón, José; et al.; Mechanistic framework for the formation of different sulfur species by electron irradiation of n -Dodecanethiol Self-Assembled monolayers on Au(111) and Au(100); American Chemical Society; Journal of Physical Chemistry C; 124; 41; 10-2020; 22591-22600
1932-7447
1932-7455
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://pubs.acs.org/doi/10.1021/acs.jpcc.0c07106
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.0c07106
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 American Chemical Society
publisher.none.fl_str_mv American Chemical 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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