Mechanistic Framework for the Formation of Different Sulfur Species by Electron Irradiation of n-Dodecanethiol Self-Assembled Monolayers on Au (111) and Au (100)

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 in...

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Autores principales: Aagaard, Natalia D., Azcárate, Julio C., Olmos-Asar, Jimena A., Mariscal, Marcelo M., Solla-Gullón, José, Zelaya, Eugenia, Fonticelli, Mariano Hernán
Formato: Articulo
Lenguaje:Inglés
Publicado: 2020
Materias:
Física
Química
Thiols
Sulfur
X-ray photoelectron spectroscopy
Irradiation
Gold
Acceso en línea:http://sedici.unlp.edu.ar/handle/10915/136294
Aporte de:
SEDICI (UNLP) de Universidad Nacional de La Plata
id I19-R120-10915-136294
record_format dspace
institution Universidad Nacional de La Plata
institution_str I-19
repository_str R-120
collection SEDICI (UNLP)
language Inglés
topic Física
Química
Thiols
Sulfur
X-ray photoelectron spectroscopy
Irradiation
Gold
spellingShingle Física
Química
Thiols
Sulfur
X-ray photoelectron spectroscopy
Irradiation
Gold
Aagaard, Natalia D.
Azcárate, Julio C.
Olmos-Asar, Jimena A.
Mariscal, Marcelo M.
Solla-Gullón, José
Zelaya, Eugenia
Fonticelli, Mariano Hernán
Mechanistic Framework for the Formation of Different Sulfur Species by Electron Irradiation of n-Dodecanethiol Self-Assembled Monolayers on Au (111) and Au (100)
topic_facet Física
Química
Thiols
Sulfur
X-ray photoelectron spectroscopy
Irradiation
Gold
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.
format Articulo
Articulo
author Aagaard, Natalia D.
Azcárate, Julio C.
Olmos-Asar, Jimena A.
Mariscal, Marcelo M.
Solla-Gullón, José
Zelaya, Eugenia
Fonticelli, Mariano Hernán
author_facet Aagaard, Natalia D.
Azcárate, Julio C.
Olmos-Asar, Jimena A.
Mariscal, Marcelo M.
Solla-Gullón, José
Zelaya, Eugenia
Fonticelli, Mariano Hernán
author_sort Aagaard, Natalia D.
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)
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)
publishDate 2020
url http://sedici.unlp.edu.ar/handle/10915/136294
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