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
- Institución
- Universidad Nacional de La Plata
- OAI Identificador
- oai:sedici.unlp.edu.ar:10915/136294
Ver los metadatos del registro completo
id |
SEDICI_082eb5646e0a575f0f953785765585a6 |
---|---|
oai_identifier_str |
oai:sedici.unlp.edu.ar:10915/136294 |
network_acronym_str |
SEDICI |
repository_id_str |
1329 |
network_name_str |
SEDICI (UNLP) |
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 Articulo 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://sedici.unlp.edu.ar/handle/10915/136294 |
url |
http://sedici.unlp.edu.ar/handle/10915/136294 |
dc.language.none.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
info:eu-repo/semantics/altIdentifier/issn/1932-7447 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 http://creativecommons.org/licenses/by-nc-sa/4.0/ Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0) |
eu_rights_str_mv |
openAccess |
rights_invalid_str_mv |
http://creativecommons.org/licenses/by-nc-sa/4.0/ Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0) |
dc.format.none.fl_str_mv |
application/pdf 22591-22600 |
dc.source.none.fl_str_mv |
reponame:SEDICI (UNLP) instname:Universidad Nacional de La Plata instacron:UNLP |
reponame_str |
SEDICI (UNLP) |
collection |
SEDICI (UNLP) |
instname_str |
Universidad Nacional de La Plata |
instacron_str |
UNLP |
institution |
UNLP |
repository.name.fl_str_mv |
SEDICI (UNLP) - Universidad Nacional de La Plata |
repository.mail.fl_str_mv |
alira@sedici.unlp.edu.ar |
_version_ |
1842260542959386624 |
score |
13.13397 |