Thiolate-Bonded Self-Assembled Monolayers on Ni(111): Bonding Strength, Structure, and Stability

Autores
Blobner, F.; Abufager, Paula Natalia; Han, R.; Bauer, J.; Duncan, D. A.; Maurer, R. J.; Reuter, K.; Feulner, P.; Allegretti, F.
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Self-assembled monolayers (SAMs) grown on surfaces of ferromagnetic metals have attracted increasing attention as they can act as corrosion inhibitors on easily oxidizable transition metals and are potentially relevant for application in spintronics. We have performed a model study of aromatic thiol SAMs grown on atomically flat Ni(111) by means of synchrotron-based X-ray photoelectron spectrosco- py, X-ray absorption spectroscopy, and density functional theory. Our analysis demonstrates that well-defined bonding through the sulfur headgroup of the molecules (thiolate bonding) can be established at 200 K. However, the bonding configuration is metastable: breaking of the C−S bond and subsequent chemisorption of both fragments on the Ni surface decreases the total energy. The low activation barrier for C−S dissociation hampers the formation of room-temperature-stable monolayers. In addition, we show that end groups with a strong affinity to the nickel substrate can severely modify the global pattern of interaction of the thiol molecules with the surface upon adsorption.
Fil: Blobner, F.. Technische Universitat Munchen; Alemania
Fil: Abufager, Paula Natalia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Física de Rosario (i); Argentina
Fil: Han, R.. Technische Universitat Munchen; Alemania
Fil: Bauer, J.. Technische Universitat Munchen; Alemania
Fil: Duncan, D. A.. Technische Universitat Munchen; Alemania
Fil: Maurer, R. J.. Technische Universitat Munchen; Alemania
Fil: Reuter, K.. Technische Universitat Munchen; Alemania
Fil: Feulner, P.. Technische Universitat Munchen; Alemania
Fil: Allegretti, F.. Technische Universitat Munchen; Alemania
Materia
Sam
Tiolatos
Niquel
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:11336/6162
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/6162
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Thiolate-Bonded Self-Assembled Monolayers on Ni(111): Bonding Strength, Structure, and StabilityBlobner, F.Abufager, Paula NataliaHan, R.Bauer, J.Duncan, D. A.Maurer, R. J.Reuter, K.Feulner, P.Allegretti, F.SamTiolatosNiquelhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1Self-assembled monolayers (SAMs) grown on surfaces of ferromagnetic metals have attracted increasing attention as they can act as corrosion inhibitors on easily oxidizable transition metals and are potentially relevant for application in spintronics. We have performed a model study of aromatic thiol SAMs grown on atomically flat Ni(111) by means of synchrotron-based X-ray photoelectron spectrosco- py, X-ray absorption spectroscopy, and density functional theory. Our analysis demonstrates that well-defined bonding through the sulfur headgroup of the molecules (thiolate bonding) can be established at 200 K. However, the bonding configuration is metastable: breaking of the C−S bond and subsequent chemisorption of both fragments on the Ni surface decreases the total energy. The low activation barrier for C−S dissociation hampers the formation of room-temperature-stable monolayers. In addition, we show that end groups with a strong affinity to the nickel substrate can severely modify the global pattern of interaction of the thiol molecules with the surface upon adsorption.Fil: Blobner, F.. Technische Universitat Munchen; AlemaniaFil: Abufager, Paula Natalia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Física de Rosario (i); ArgentinaFil: Han, R.. Technische Universitat Munchen; AlemaniaFil: Bauer, J.. Technische Universitat Munchen; AlemaniaFil: Duncan, D. A.. Technische Universitat Munchen; AlemaniaFil: Maurer, R. J.. Technische Universitat Munchen; AlemaniaFil: Reuter, K.. Technische Universitat Munchen; AlemaniaFil: Feulner, P.. Technische Universitat Munchen; AlemaniaFil: Allegretti, F.. Technische Universitat Munchen; AlemaniaAmerican Chemical Society2015-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/6162Blobner, F.; Abufager, Paula Natalia; Han, R.; Bauer, J.; Duncan, D. A.; et al.; Thiolate-Bonded Self-Assembled Monolayers on Ni(111): Bonding Strength, Structure, and Stability; American Chemical Society; Journal of Physical Chemistry C; 119; 27; 6-2015; 15455-154681932-7447enginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/acs.jpcc.5b04351info:eu-repo/semantics/altIdentifier/doi/info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.5b04351info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2026-01-14T12:16:01Zoai:ri.conicet.gov.ar:11336/6162instacron: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:34982026-01-14 12:16:01.392CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Thiolate-Bonded Self-Assembled Monolayers on Ni(111): Bonding Strength, Structure, and Stability
title Thiolate-Bonded Self-Assembled Monolayers on Ni(111): Bonding Strength, Structure, and Stability
spellingShingle Thiolate-Bonded Self-Assembled Monolayers on Ni(111): Bonding Strength, Structure, and Stability
Blobner, F.
Sam
Tiolatos
Niquel
title_short Thiolate-Bonded Self-Assembled Monolayers on Ni(111): Bonding Strength, Structure, and Stability
title_full Thiolate-Bonded Self-Assembled Monolayers on Ni(111): Bonding Strength, Structure, and Stability
title_fullStr Thiolate-Bonded Self-Assembled Monolayers on Ni(111): Bonding Strength, Structure, and Stability
title_full_unstemmed Thiolate-Bonded Self-Assembled Monolayers on Ni(111): Bonding Strength, Structure, and Stability
title_sort Thiolate-Bonded Self-Assembled Monolayers on Ni(111): Bonding Strength, Structure, and Stability
dc.creator.none.fl_str_mv Blobner, F.
Abufager, Paula Natalia
Han, R.
Bauer, J.
Duncan, D. A.
Maurer, R. J.
Reuter, K.
Feulner, P.
Allegretti, F.
author Blobner, F.
author_facet Blobner, F.
Abufager, Paula Natalia
Han, R.
Bauer, J.
Duncan, D. A.
Maurer, R. J.
Reuter, K.
Feulner, P.
Allegretti, F.
author_role author
author2 Abufager, Paula Natalia
Han, R.
Bauer, J.
Duncan, D. A.
Maurer, R. J.
Reuter, K.
Feulner, P.
Allegretti, F.
author2_role author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Sam
Tiolatos
Niquel
topic Sam
Tiolatos
Niquel
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Self-assembled monolayers (SAMs) grown on surfaces of ferromagnetic metals have attracted increasing attention as they can act as corrosion inhibitors on easily oxidizable transition metals and are potentially relevant for application in spintronics. We have performed a model study of aromatic thiol SAMs grown on atomically flat Ni(111) by means of synchrotron-based X-ray photoelectron spectrosco- py, X-ray absorption spectroscopy, and density functional theory. Our analysis demonstrates that well-defined bonding through the sulfur headgroup of the molecules (thiolate bonding) can be established at 200 K. However, the bonding configuration is metastable: breaking of the C−S bond and subsequent chemisorption of both fragments on the Ni surface decreases the total energy. The low activation barrier for C−S dissociation hampers the formation of room-temperature-stable monolayers. In addition, we show that end groups with a strong affinity to the nickel substrate can severely modify the global pattern of interaction of the thiol molecules with the surface upon adsorption.
Fil: Blobner, F.. Technische Universitat Munchen; Alemania
Fil: Abufager, Paula Natalia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Física de Rosario (i); Argentina
Fil: Han, R.. Technische Universitat Munchen; Alemania
Fil: Bauer, J.. Technische Universitat Munchen; Alemania
Fil: Duncan, D. A.. Technische Universitat Munchen; Alemania
Fil: Maurer, R. J.. Technische Universitat Munchen; Alemania
Fil: Reuter, K.. Technische Universitat Munchen; Alemania
Fil: Feulner, P.. Technische Universitat Munchen; Alemania
Fil: Allegretti, F.. Technische Universitat Munchen; Alemania
description Self-assembled monolayers (SAMs) grown on surfaces of ferromagnetic metals have attracted increasing attention as they can act as corrosion inhibitors on easily oxidizable transition metals and are potentially relevant for application in spintronics. We have performed a model study of aromatic thiol SAMs grown on atomically flat Ni(111) by means of synchrotron-based X-ray photoelectron spectrosco- py, X-ray absorption spectroscopy, and density functional theory. Our analysis demonstrates that well-defined bonding through the sulfur headgroup of the molecules (thiolate bonding) can be established at 200 K. However, the bonding configuration is metastable: breaking of the C−S bond and subsequent chemisorption of both fragments on the Ni surface decreases the total energy. The low activation barrier for C−S dissociation hampers the formation of room-temperature-stable monolayers. In addition, we show that end groups with a strong affinity to the nickel substrate can severely modify the global pattern of interaction of the thiol molecules with the surface upon adsorption.
publishDate 2015
dc.date.none.fl_str_mv 2015-06
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/11336/6162
Blobner, F.; Abufager, Paula Natalia; Han, R.; Bauer, J.; Duncan, D. A.; et al.; Thiolate-Bonded Self-Assembled Monolayers on Ni(111): Bonding Strength, Structure, and Stability; American Chemical Society; Journal of Physical Chemistry C; 119; 27; 6-2015; 15455-15468
1932-7447
url http://hdl.handle.net/11336/6162
identifier_str_mv Blobner, F.; Abufager, Paula Natalia; Han, R.; Bauer, J.; Duncan, D. A.; et al.; Thiolate-Bonded Self-Assembled Monolayers on Ni(111): Bonding Strength, Structure, and Stability; American Chemical Society; Journal of Physical Chemistry C; 119; 27; 6-2015; 15455-15468
1932-7447
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/acs.jpcc.5b04351
info:eu-repo/semantics/altIdentifier/doi/
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.5b04351
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
_version_ 1854321595676360704
score 13.113929

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