A New Approach for the Calculation on the Entropic and Free Energy Contributions to Underpotential Deposition

Autores
Farigliano, Lucas Martín; Villarreal, Marcos Ariel; Oviedo, Oscar Alejandro; Leiva, Ezequiel Pedro M.
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In the present work we have studied the electrochemical nonpseudomorphic formation of Pb bidimensional structures on Au(111) surfaces. Based on the two-phase thermodynamic method, we have analyzed, from a computational perspective, entropic and energetic contributions to underpotential deposition. The occurrence of incommensurate nanophase formation, rotation of the adsorbate with respect to the substrate, and the effect of expansion and compression of the Pb monolayer were also analyzed. Our results show that the entropic contribution to monolayer underpotential deposition of Pb on Au(111) at room temperature is approximately 20% of the total free energy excess. For very small clusters, this contribution increases up to 45%. Simulations show that in the early stages of formation, Pb nanophases grow without rotation. When the size of the Pb islands is close 100 atoms, a rotation process takes places. At relatively high coverage, a strong lateral compression of Pb monolayer sets on, evidenced by a sharp decrease in the distance between nearest neighbors.
Fil: Farigliano, Lucas Martín. 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: Villarreal, Marcos Ariel. 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: Oviedo, Oscar Alejandro. 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: Leiva, Ezequiel Pedro M.. 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
Materia
Entropy Contribution
Two-Phase Method
Underpotential Deposition
Lead/Gold
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:11336/31361
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/31361
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling A New Approach for the Calculation on the Entropic and Free Energy Contributions to Underpotential DepositionFarigliano, Lucas MartínVillarreal, Marcos ArielOviedo, Oscar AlejandroLeiva, Ezequiel Pedro M.Entropy ContributionTwo-Phase MethodUnderpotential DepositionLead/Goldhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1In the present work we have studied the electrochemical nonpseudomorphic formation of Pb bidimensional structures on Au(111) surfaces. Based on the two-phase thermodynamic method, we have analyzed, from a computational perspective, entropic and energetic contributions to underpotential deposition. The occurrence of incommensurate nanophase formation, rotation of the adsorbate with respect to the substrate, and the effect of expansion and compression of the Pb monolayer were also analyzed. Our results show that the entropic contribution to monolayer underpotential deposition of Pb on Au(111) at room temperature is approximately 20% of the total free energy excess. For very small clusters, this contribution increases up to 45%. Simulations show that in the early stages of formation, Pb nanophases grow without rotation. When the size of the Pb islands is close 100 atoms, a rotation process takes places. At relatively high coverage, a strong lateral compression of Pb monolayer sets on, evidenced by a sharp decrease in the distance between nearest neighbors.Fil: Farigliano, Lucas Martín. 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: Villarreal, Marcos Ariel. 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: Oviedo, Oscar Alejandro. 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: Leiva, Ezequiel Pedro M.. 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; ArgentinaElectrochemical Society2014-04info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/31361Leiva, Ezequiel Pedro M.; Oviedo, Oscar Alejandro; Villarreal, Marcos Ariel; Farigliano, Lucas Martín; A New Approach for the Calculation on the Entropic and Free Energy Contributions to Underpotential Deposition; Electrochemical Society; Electrochemical Society Transaction; 58; 32; 4-2014; 3-201938-5862CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1149/05832.0003ecstinfo:eu-repo/semantics/altIdentifier/url/http://ecst.ecsdl.org/content/58/32/3info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:15:58Zoai:ri.conicet.gov.ar:11336/31361instacron: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:34982025-10-22 11:15:59.271CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv A New Approach for the Calculation on the Entropic and Free Energy Contributions to Underpotential Deposition
title A New Approach for the Calculation on the Entropic and Free Energy Contributions to Underpotential Deposition
spellingShingle A New Approach for the Calculation on the Entropic and Free Energy Contributions to Underpotential Deposition
Farigliano, Lucas Martín
Entropy Contribution
Two-Phase Method
Underpotential Deposition
Lead/Gold
title_short A New Approach for the Calculation on the Entropic and Free Energy Contributions to Underpotential Deposition
title_full A New Approach for the Calculation on the Entropic and Free Energy Contributions to Underpotential Deposition
title_fullStr A New Approach for the Calculation on the Entropic and Free Energy Contributions to Underpotential Deposition
title_full_unstemmed A New Approach for the Calculation on the Entropic and Free Energy Contributions to Underpotential Deposition
title_sort A New Approach for the Calculation on the Entropic and Free Energy Contributions to Underpotential Deposition
dc.creator.none.fl_str_mv Farigliano, Lucas Martín
Villarreal, Marcos Ariel
Oviedo, Oscar Alejandro
Leiva, Ezequiel Pedro M.
author Farigliano, Lucas Martín
author_facet Farigliano, Lucas Martín
Villarreal, Marcos Ariel
Oviedo, Oscar Alejandro
Leiva, Ezequiel Pedro M.
author_role author
author2 Villarreal, Marcos Ariel
Oviedo, Oscar Alejandro
Leiva, Ezequiel Pedro M.
author2_role author
author
author
dc.subject.none.fl_str_mv Entropy Contribution
Two-Phase Method
Underpotential Deposition
Lead/Gold
topic Entropy Contribution
Two-Phase Method
Underpotential Deposition
Lead/Gold
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv In the present work we have studied the electrochemical nonpseudomorphic formation of Pb bidimensional structures on Au(111) surfaces. Based on the two-phase thermodynamic method, we have analyzed, from a computational perspective, entropic and energetic contributions to underpotential deposition. The occurrence of incommensurate nanophase formation, rotation of the adsorbate with respect to the substrate, and the effect of expansion and compression of the Pb monolayer were also analyzed. Our results show that the entropic contribution to monolayer underpotential deposition of Pb on Au(111) at room temperature is approximately 20% of the total free energy excess. For very small clusters, this contribution increases up to 45%. Simulations show that in the early stages of formation, Pb nanophases grow without rotation. When the size of the Pb islands is close 100 atoms, a rotation process takes places. At relatively high coverage, a strong lateral compression of Pb monolayer sets on, evidenced by a sharp decrease in the distance between nearest neighbors.
Fil: Farigliano, Lucas Martín. 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: Villarreal, Marcos Ariel. 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: Oviedo, Oscar Alejandro. 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: Leiva, Ezequiel Pedro M.. 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
description In the present work we have studied the electrochemical nonpseudomorphic formation of Pb bidimensional structures on Au(111) surfaces. Based on the two-phase thermodynamic method, we have analyzed, from a computational perspective, entropic and energetic contributions to underpotential deposition. The occurrence of incommensurate nanophase formation, rotation of the adsorbate with respect to the substrate, and the effect of expansion and compression of the Pb monolayer were also analyzed. Our results show that the entropic contribution to monolayer underpotential deposition of Pb on Au(111) at room temperature is approximately 20% of the total free energy excess. For very small clusters, this contribution increases up to 45%. Simulations show that in the early stages of formation, Pb nanophases grow without rotation. When the size of the Pb islands is close 100 atoms, a rotation process takes places. At relatively high coverage, a strong lateral compression of Pb monolayer sets on, evidenced by a sharp decrease in the distance between nearest neighbors.
publishDate 2014
dc.date.none.fl_str_mv 2014-04
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/11336/31361
Leiva, Ezequiel Pedro M.; Oviedo, Oscar Alejandro; Villarreal, Marcos Ariel; Farigliano, Lucas Martín; A New Approach for the Calculation on the Entropic and Free Energy Contributions to Underpotential Deposition; Electrochemical Society; Electrochemical Society Transaction; 58; 32; 4-2014; 3-20
1938-5862
CONICET Digital
CONICET
url http://hdl.handle.net/11336/31361
identifier_str_mv Leiva, Ezequiel Pedro M.; Oviedo, Oscar Alejandro; Villarreal, Marcos Ariel; Farigliano, Lucas Martín; A New Approach for the Calculation on the Entropic and Free Energy Contributions to Underpotential Deposition; Electrochemical Society; Electrochemical Society Transaction; 58; 32; 4-2014; 3-20
1938-5862
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1149/05832.0003ecst
info:eu-repo/semantics/altIdentifier/url/http://ecst.ecsdl.org/content/58/32/3
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
application/pdf
dc.publisher.none.fl_str_mv Electrochemical Society
publisher.none.fl_str_mv Electrochemical 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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score 12.982451

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