Comparison of the Kinetics of Electron Transfer in the Diffusion Limit for the Singlet and Triplet Quenching of Eosin Y by Quinones

Autores
Bertolotti, Sonia Graciela; Montejano, Hernan Alfredo; Previtali, Carlos Mario
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Electron transfer (ET) rate constants were determined by means of lifetime measurements for the fluorescence quenching and by laser flash photolysis for the triplet quenching of the dye eosin Y by benzoquinones in acetonitrile. The results represent a new aspect of the dependence of the rate constants with the driving force in the diffusion limit region. That is, the rate constants for singlet quenching in the highly negative region of DGet do not decrease as predicted by Marcus theory, but rather show a small positive dependence on the driving force. However, it is found that, in the same free energy range, the triplet rate constants are lower than those for the singlet process. They also increase with the exergonicity of the reaction, but the dependence with DGet is less marked than that found for the singlet reaction. Even at a Gibbs energy change of 1.0 eV the triplet quenching rate constants do not reach the theoretical diffusion limit. The results are analyzed using the current theories for diffusionmediated ET reactions.
Fil: Bertolotti, Sonia Graciela. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Montejano, Hernan Alfredo. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Previtali, Carlos Mario. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Materia
Electron Transfer
Eosin
Quinones
Singlet And Triplet States
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:11336/22940
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Comparison of the Kinetics of Electron Transfer in the Diffusion Limit for the Singlet and Triplet Quenching of Eosin Y by QuinonesBertolotti, Sonia GracielaMontejano, Hernan AlfredoPrevitali, Carlos MarioElectron TransferEosinQuinonesSinglet And Triplet Stateshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Electron transfer (ET) rate constants were determined by means of lifetime measurements for the fluorescence quenching and by laser flash photolysis for the triplet quenching of the dye eosin Y by benzoquinones in acetonitrile. The results represent a new aspect of the dependence of the rate constants with the driving force in the diffusion limit region. That is, the rate constants for singlet quenching in the highly negative region of DGet do not decrease as predicted by Marcus theory, but rather show a small positive dependence on the driving force. However, it is found that, in the same free energy range, the triplet rate constants are lower than those for the singlet process. They also increase with the exergonicity of the reaction, but the dependence with DGet is less marked than that found for the singlet reaction. Even at a Gibbs energy change of 1.0 eV the triplet quenching rate constants do not reach the theoretical diffusion limit. The results are analyzed using the current theories for diffusionmediated ET reactions.Fil: Bertolotti, Sonia Graciela. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Montejano, Hernan Alfredo. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Previtali, Carlos Mario. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaWiley2013-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/22940Bertolotti, Sonia Graciela; Montejano, Hernan Alfredo; Previtali, Carlos Mario; Comparison of the Kinetics of Electron Transfer in the Diffusion Limit for the Singlet and Triplet Quenching of Eosin Y by Quinones; Wiley; Photochemistry and Photobiology; 89; 6; 6-2013; 1442-14470031-8655CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1111/php.12089info:eu-repo/semantics/altIdentifier/url/http://onlinelibrary.wiley.com/doi/10.1111/php.12089/abstractinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:02:53Zoai:ri.conicet.gov.ar:11336/22940instacron: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 11:02:53.83CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Comparison of the Kinetics of Electron Transfer in the Diffusion Limit for the Singlet and Triplet Quenching of Eosin Y by Quinones
title Comparison of the Kinetics of Electron Transfer in the Diffusion Limit for the Singlet and Triplet Quenching of Eosin Y by Quinones
spellingShingle Comparison of the Kinetics of Electron Transfer in the Diffusion Limit for the Singlet and Triplet Quenching of Eosin Y by Quinones
Bertolotti, Sonia Graciela
Electron Transfer
Eosin
Quinones
Singlet And Triplet States
title_short Comparison of the Kinetics of Electron Transfer in the Diffusion Limit for the Singlet and Triplet Quenching of Eosin Y by Quinones
title_full Comparison of the Kinetics of Electron Transfer in the Diffusion Limit for the Singlet and Triplet Quenching of Eosin Y by Quinones
title_fullStr Comparison of the Kinetics of Electron Transfer in the Diffusion Limit for the Singlet and Triplet Quenching of Eosin Y by Quinones
title_full_unstemmed Comparison of the Kinetics of Electron Transfer in the Diffusion Limit for the Singlet and Triplet Quenching of Eosin Y by Quinones
title_sort Comparison of the Kinetics of Electron Transfer in the Diffusion Limit for the Singlet and Triplet Quenching of Eosin Y by Quinones
dc.creator.none.fl_str_mv Bertolotti, Sonia Graciela
Montejano, Hernan Alfredo
Previtali, Carlos Mario
author Bertolotti, Sonia Graciela
author_facet Bertolotti, Sonia Graciela
Montejano, Hernan Alfredo
Previtali, Carlos Mario
author_role author
author2 Montejano, Hernan Alfredo
Previtali, Carlos Mario
author2_role author
author
dc.subject.none.fl_str_mv Electron Transfer
Eosin
Quinones
Singlet And Triplet States
topic Electron Transfer
Eosin
Quinones
Singlet And Triplet States
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Electron transfer (ET) rate constants were determined by means of lifetime measurements for the fluorescence quenching and by laser flash photolysis for the triplet quenching of the dye eosin Y by benzoquinones in acetonitrile. The results represent a new aspect of the dependence of the rate constants with the driving force in the diffusion limit region. That is, the rate constants for singlet quenching in the highly negative region of DGet do not decrease as predicted by Marcus theory, but rather show a small positive dependence on the driving force. However, it is found that, in the same free energy range, the triplet rate constants are lower than those for the singlet process. They also increase with the exergonicity of the reaction, but the dependence with DGet is less marked than that found for the singlet reaction. Even at a Gibbs energy change of 1.0 eV the triplet quenching rate constants do not reach the theoretical diffusion limit. The results are analyzed using the current theories for diffusionmediated ET reactions.
Fil: Bertolotti, Sonia Graciela. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Montejano, Hernan Alfredo. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Previtali, Carlos Mario. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
description Electron transfer (ET) rate constants were determined by means of lifetime measurements for the fluorescence quenching and by laser flash photolysis for the triplet quenching of the dye eosin Y by benzoquinones in acetonitrile. The results represent a new aspect of the dependence of the rate constants with the driving force in the diffusion limit region. That is, the rate constants for singlet quenching in the highly negative region of DGet do not decrease as predicted by Marcus theory, but rather show a small positive dependence on the driving force. However, it is found that, in the same free energy range, the triplet rate constants are lower than those for the singlet process. They also increase with the exergonicity of the reaction, but the dependence with DGet is less marked than that found for the singlet reaction. Even at a Gibbs energy change of 1.0 eV the triplet quenching rate constants do not reach the theoretical diffusion limit. The results are analyzed using the current theories for diffusionmediated ET reactions.
publishDate 2013
dc.date.none.fl_str_mv 2013-06
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/11336/22940
Bertolotti, Sonia Graciela; Montejano, Hernan Alfredo; Previtali, Carlos Mario; Comparison of the Kinetics of Electron Transfer in the Diffusion Limit for the Singlet and Triplet Quenching of Eosin Y by Quinones; Wiley; Photochemistry and Photobiology; 89; 6; 6-2013; 1442-1447
0031-8655
CONICET Digital
CONICET
url http://hdl.handle.net/11336/22940
identifier_str_mv Bertolotti, Sonia Graciela; Montejano, Hernan Alfredo; Previtali, Carlos Mario; Comparison of the Kinetics of Electron Transfer in the Diffusion Limit for the Singlet and Triplet Quenching of Eosin Y by Quinones; Wiley; Photochemistry and Photobiology; 89; 6; 6-2013; 1442-1447
0031-8655
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1111/php.12089
info:eu-repo/semantics/altIdentifier/url/http://onlinelibrary.wiley.com/doi/10.1111/php.12089/abstract
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
application/pdf
dc.publisher.none.fl_str_mv Wiley
publisher.none.fl_str_mv Wiley
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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