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 D.; Azcárate, Julio C.; Olmos-Asar, Jimena A.; Mariscal, Marcelo M.; Solla-Gullón, José; Zelaya, Eugenia; Fonticelli, Mariano Hernán
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 C═C 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.
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas
Materia
Física
Química
Thiols
Sulfur
X-ray photoelectron spectroscopy
Irradiation
Gold
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by-nc-sa/4.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/136294

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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 D.Azcárate, Julio C.Olmos-Asar, Jimena A.Mariscal, Marcelo M.Solla-Gullón, JoséZelaya, EugeniaFonticelli, Mariano HernánFísicaQuímicaThiolsSulfurX-ray photoelectron spectroscopyIrradiationGoldThe 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 C═C 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.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas2020info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf22591-22600http://sedici.unlp.edu.ar/handle/10915/136294enginfo:eu-repo/semantics/altIdentifier/issn/1932-7447info:eu-repo/semantics/altIdentifier/issn/1932-7455info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.0c07106info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-sa/4.0/Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-09-03T11:04:28Zoai:sedici.unlp.edu.ar:10915/136294Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-03 11:04:28.254SEDICI (UNLP) - Universidad Nacional de La Platafalse
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 D.
Física
Química
Thiols
Sulfur
X-ray photoelectron spectroscopy
Irradiation
Gold
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 D.
Azcárate, Julio C.
Olmos-Asar, Jimena A.
Mariscal, Marcelo M.
Solla-Gullón, José
Zelaya, Eugenia
Fonticelli, Mariano Hernán
author Aagaard, Natalia D.
author_facet Aagaard, Natalia D.
Azcárate, Julio C.
Olmos-Asar, Jimena A.
Mariscal, Marcelo M.
Solla-Gullón, José
Zelaya, Eugenia
Fonticelli, Mariano Hernán
author_role author
author2 Azcárate, Julio C.
Olmos-Asar, Jimena A.
Mariscal, Marcelo M.
Solla-Gullón, José
Zelaya, Eugenia
Fonticelli, Mariano Hernán
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Física
Química
Thiols
Sulfur
X-ray photoelectron spectroscopy
Irradiation
Gold
topic Física
Química
Thiols
Sulfur
X-ray photoelectron spectroscopy
Irradiation
Gold
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 C═C 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.
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas
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 C═C 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
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
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info:eu-repo/semantics/altIdentifier/issn/1932-7455
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.0c07106
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
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Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
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Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
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