Quantum theory of interfacial tension quantitatively predicts spontaneous charging of nonpolar aqueous interfaces

Autores
Fernandez, Ariel
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The spontaneous negative charging of aqueous nonpolar interfaces has eluded quantitative first-principle prediction, possibly because it steadfastly challenges the classical Debye dielectric picture. In this work we show that quantitative prediction requires a substantive revision of Debye?s linear dielectric ansatzto incorporate an anomalous polarization component yielding electrostatic energy stored as interfacial tension and detailed enough to account for the differences in electronic structure between water and its ionized states. The minimization of this interfacial tension is due to a quantum effect resulting in the reduction in hydrogen-bond frustration that takes place upon hydroxide ion adsorption. The quantitative predictions are validated vis-à-vis measurements of the free energy change associated with hydroxide adsorption obtained using sum-frequency vibrational spectroscopy.
Fil: Fernandez, Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Saavedra 15. Instituto Argentino de Matemática Alberto Calderon; Argentina. Collegium Basilea; Suiza
Materia
Aqueous Interface
Statistical Mechanics
Quantum Mechanics
Hydrogenated Graphene
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:11336/18961
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/18961
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Quantum theory of interfacial tension quantitatively predicts spontaneous charging of nonpolar aqueous interfacesFernandez, ArielAqueous InterfaceStatistical MechanicsQuantum MechanicsHydrogenated Graphenehttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1The spontaneous negative charging of aqueous nonpolar interfaces has eluded quantitative first-principle prediction, possibly because it steadfastly challenges the classical Debye dielectric picture. In this work we show that quantitative prediction requires a substantive revision of Debye?s linear dielectric ansatzto incorporate an anomalous polarization component yielding electrostatic energy stored as interfacial tension and detailed enough to account for the differences in electronic structure between water and its ionized states. The minimization of this interfacial tension is due to a quantum effect resulting in the reduction in hydrogen-bond frustration that takes place upon hydroxide ion adsorption. The quantitative predictions are validated vis-à-vis measurements of the free energy change associated with hydroxide adsorption obtained using sum-frequency vibrational spectroscopy.Fil: Fernandez, Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Saavedra 15. Instituto Argentino de Matemática Alberto Calderon; Argentina. Collegium Basilea; SuizaElsevier Science2015-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/18961Fernandez, Ariel; Quantum theory of interfacial tension quantitatively predicts spontaneous charging of nonpolar aqueous interfaces; Elsevier Science; Physics Letters A; 379; 39; 7-2015; 2405-24080375-9601CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0375960115006295info:eu-repo/semantics/altIdentifier/doi/10.1016/j.physleta.2015.07.027info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T15:15:14Zoai:ri.conicet.gov.ar:11336/18961instacron: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:34982025-10-15 15:15:15.137CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Quantum theory of interfacial tension quantitatively predicts spontaneous charging of nonpolar aqueous interfaces
title Quantum theory of interfacial tension quantitatively predicts spontaneous charging of nonpolar aqueous interfaces
spellingShingle Quantum theory of interfacial tension quantitatively predicts spontaneous charging of nonpolar aqueous interfaces
Fernandez, Ariel
Aqueous Interface
Statistical Mechanics
Quantum Mechanics
Hydrogenated Graphene
title_short Quantum theory of interfacial tension quantitatively predicts spontaneous charging of nonpolar aqueous interfaces
title_full Quantum theory of interfacial tension quantitatively predicts spontaneous charging of nonpolar aqueous interfaces
title_fullStr Quantum theory of interfacial tension quantitatively predicts spontaneous charging of nonpolar aqueous interfaces
title_full_unstemmed Quantum theory of interfacial tension quantitatively predicts spontaneous charging of nonpolar aqueous interfaces
title_sort Quantum theory of interfacial tension quantitatively predicts spontaneous charging of nonpolar aqueous interfaces
dc.creator.none.fl_str_mv Fernandez, Ariel
author Fernandez, Ariel
author_facet Fernandez, Ariel
author_role author
dc.subject.none.fl_str_mv Aqueous Interface
Statistical Mechanics
Quantum Mechanics
Hydrogenated Graphene
topic Aqueous Interface
Statistical Mechanics
Quantum Mechanics
Hydrogenated Graphene
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The spontaneous negative charging of aqueous nonpolar interfaces has eluded quantitative first-principle prediction, possibly because it steadfastly challenges the classical Debye dielectric picture. In this work we show that quantitative prediction requires a substantive revision of Debye?s linear dielectric ansatzto incorporate an anomalous polarization component yielding electrostatic energy stored as interfacial tension and detailed enough to account for the differences in electronic structure between water and its ionized states. The minimization of this interfacial tension is due to a quantum effect resulting in the reduction in hydrogen-bond frustration that takes place upon hydroxide ion adsorption. The quantitative predictions are validated vis-à-vis measurements of the free energy change associated with hydroxide adsorption obtained using sum-frequency vibrational spectroscopy.
Fil: Fernandez, Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Saavedra 15. Instituto Argentino de Matemática Alberto Calderon; Argentina. Collegium Basilea; Suiza
description The spontaneous negative charging of aqueous nonpolar interfaces has eluded quantitative first-principle prediction, possibly because it steadfastly challenges the classical Debye dielectric picture. In this work we show that quantitative prediction requires a substantive revision of Debye?s linear dielectric ansatzto incorporate an anomalous polarization component yielding electrostatic energy stored as interfacial tension and detailed enough to account for the differences in electronic structure between water and its ionized states. The minimization of this interfacial tension is due to a quantum effect resulting in the reduction in hydrogen-bond frustration that takes place upon hydroxide ion adsorption. The quantitative predictions are validated vis-à-vis measurements of the free energy change associated with hydroxide adsorption obtained using sum-frequency vibrational spectroscopy.
publishDate 2015
dc.date.none.fl_str_mv 2015-07
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/11336/18961
Fernandez, Ariel; Quantum theory of interfacial tension quantitatively predicts spontaneous charging of nonpolar aqueous interfaces; Elsevier Science; Physics Letters A; 379; 39; 7-2015; 2405-2408
0375-9601
CONICET Digital
CONICET
url http://hdl.handle.net/11336/18961
identifier_str_mv Fernandez, Ariel; Quantum theory of interfacial tension quantitatively predicts spontaneous charging of nonpolar aqueous interfaces; Elsevier Science; Physics Letters A; 379; 39; 7-2015; 2405-2408
0375-9601
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0375960115006295
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.physleta.2015.07.027
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 Elsevier Science
publisher.none.fl_str_mv Elsevier Science
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_ 1846083300137893888
score 13.22299

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