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

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...

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Autor: Fernandez, Ariel
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2015
País:Argentina
Institución:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/18961
Acceso en línea:http://hdl.handle.net/11336/18961
Access Level:acceso abierto
Palabra clave:Aqueous Interface
Statistical Mechanics
Quantum Mechanics
Hydrogenated Graphene
https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
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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 Técnicas2024-05-08T14:07:00Zoai: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:34982024-05-08 14:07:00.664CONICET 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
https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
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
https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
topic Aqueous Interface
Statistical Mechanics
Quantum Mechanics
Hydrogenated Graphene
https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
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
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
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 15,81155

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