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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/144374
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oai:ri.conicet.gov.ar:11336/144374 |
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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 Técnicas2025-09-03T09:49:11Zoai: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:34982025-09-03 09:49:12.221CONICET 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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1842268959116623872 |
score |
13.13397 |