Energy transfer and spatial scrambling of an exciton in a conjugated dendrimer

Autores
Ondarse Alvarez, Dianelys; Oldani, Andres Nicolas; Roitberg, A. E.; Kleiman, V.; Tretiak, Sergei; Fernández Alberti, Sebastián
Año de publicación
2018
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Photoexcitation of multichromophoric light harvesting molecules induces a number of intramolecular electronic energy relaxation and redistribution pathways that can ultimately lead to ultrafast exciton self-trapping on a single chromophore unit. We investigate the photoinduced processes that take place on a phenylene-ethynylene dendrimer, consisting of nine equivalent linear chromophore units or branches. meta-Substituted links between branches break the conjugation giving rise to weak couplings between them and to localized excitations. Our nonadiabatic excited-state molecular dynamics simulations reveal that the ultrafast internal conversion process to the lowest excited state is accompanied by an inner → outer inter-branch migration of the exciton due to the entropic bias associated with energetically equivalent conjugated segments. The electronic energy redistribution among chromophore units occurs through several possible pathways in which through-bond transport and through-space exciton hopping mechanisms can be distinguished. Besides, triple bond excitations coincide with the localization of the electronic transition densities, suggesting that the intramolecular energy redistribution is a concerted electronic and vibrational energy transfer process.
Fil: Ondarse Alvarez, Dianelys. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Oldani, Andres Nicolas. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Roitberg, A. E.. University of Florida; Estados Unidos
Fil: Kleiman, V.. University of Florida; Estados Unidos
Fil: Tretiak, Sergei. Center for Integrated Nanotechnologies; Estados Unidos
Fil: Fernández Alberti, Sebastián. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Materia
NAESMD
DENDRIMERS
CONJUGATED POLYMERS
SPATIAL SCRAMBLING
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:11336/98342
Acceder
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network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Energy transfer and spatial scrambling of an exciton in a conjugated dendrimerOndarse Alvarez, DianelysOldani, Andres NicolasRoitberg, A. E.Kleiman, V.Tretiak, SergeiFernández Alberti, SebastiánNAESMDDENDRIMERSCONJUGATED POLYMERSSPATIAL SCRAMBLINGhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Photoexcitation of multichromophoric light harvesting molecules induces a number of intramolecular electronic energy relaxation and redistribution pathways that can ultimately lead to ultrafast exciton self-trapping on a single chromophore unit. We investigate the photoinduced processes that take place on a phenylene-ethynylene dendrimer, consisting of nine equivalent linear chromophore units or branches. meta-Substituted links between branches break the conjugation giving rise to weak couplings between them and to localized excitations. Our nonadiabatic excited-state molecular dynamics simulations reveal that the ultrafast internal conversion process to the lowest excited state is accompanied by an inner → outer inter-branch migration of the exciton due to the entropic bias associated with energetically equivalent conjugated segments. The electronic energy redistribution among chromophore units occurs through several possible pathways in which through-bond transport and through-space exciton hopping mechanisms can be distinguished. Besides, triple bond excitations coincide with the localization of the electronic transition densities, suggesting that the intramolecular energy redistribution is a concerted electronic and vibrational energy transfer process.Fil: Ondarse Alvarez, Dianelys. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Oldani, Andres Nicolas. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Roitberg, A. E.. University of Florida; Estados UnidosFil: Kleiman, V.. University of Florida; Estados UnidosFil: Tretiak, Sergei. Center for Integrated Nanotechnologies; Estados UnidosFil: Fernández Alberti, Sebastián. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaRoyal Society of Chemistry2018-11info: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/11336/98342Ondarse Alvarez, Dianelys; Oldani, Andres Nicolas; Roitberg, A. E.; Kleiman, V.; Tretiak, Sergei; et al.; Energy transfer and spatial scrambling of an exciton in a conjugated dendrimer; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 20; 47; 11-2018; 29648-296601463-9076CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2018/CP/C8CP05852K#!divAbstractinfo:eu-repo/semantics/altIdentifier/doi/10.1039/c8cp05852kinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:00:43Zoai:ri.conicet.gov.ar:11336/98342instacron: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:34982025-09-03 10:00:44.131CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Energy transfer and spatial scrambling of an exciton in a conjugated dendrimer
title Energy transfer and spatial scrambling of an exciton in a conjugated dendrimer
spellingShingle Energy transfer and spatial scrambling of an exciton in a conjugated dendrimer
Ondarse Alvarez, Dianelys
NAESMD
DENDRIMERS
CONJUGATED POLYMERS
SPATIAL SCRAMBLING
title_short Energy transfer and spatial scrambling of an exciton in a conjugated dendrimer
title_full Energy transfer and spatial scrambling of an exciton in a conjugated dendrimer
title_fullStr Energy transfer and spatial scrambling of an exciton in a conjugated dendrimer
title_full_unstemmed Energy transfer and spatial scrambling of an exciton in a conjugated dendrimer
title_sort Energy transfer and spatial scrambling of an exciton in a conjugated dendrimer
dc.creator.none.fl_str_mv Ondarse Alvarez, Dianelys
Oldani, Andres Nicolas
Roitberg, A. E.
Kleiman, V.
Tretiak, Sergei
Fernández Alberti, Sebastián
author Ondarse Alvarez, Dianelys
author_facet Ondarse Alvarez, Dianelys
Oldani, Andres Nicolas
Roitberg, A. E.
Kleiman, V.
Tretiak, Sergei
Fernández Alberti, Sebastián
author_role author
author2 Oldani, Andres Nicolas
Roitberg, A. E.
Kleiman, V.
Tretiak, Sergei
Fernández Alberti, Sebastián
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv NAESMD
DENDRIMERS
CONJUGATED POLYMERS
SPATIAL SCRAMBLING
topic NAESMD
DENDRIMERS
CONJUGATED POLYMERS
SPATIAL SCRAMBLING
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Photoexcitation of multichromophoric light harvesting molecules induces a number of intramolecular electronic energy relaxation and redistribution pathways that can ultimately lead to ultrafast exciton self-trapping on a single chromophore unit. We investigate the photoinduced processes that take place on a phenylene-ethynylene dendrimer, consisting of nine equivalent linear chromophore units or branches. meta-Substituted links between branches break the conjugation giving rise to weak couplings between them and to localized excitations. Our nonadiabatic excited-state molecular dynamics simulations reveal that the ultrafast internal conversion process to the lowest excited state is accompanied by an inner → outer inter-branch migration of the exciton due to the entropic bias associated with energetically equivalent conjugated segments. The electronic energy redistribution among chromophore units occurs through several possible pathways in which through-bond transport and through-space exciton hopping mechanisms can be distinguished. Besides, triple bond excitations coincide with the localization of the electronic transition densities, suggesting that the intramolecular energy redistribution is a concerted electronic and vibrational energy transfer process.
Fil: Ondarse Alvarez, Dianelys. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Oldani, Andres Nicolas. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Roitberg, A. E.. University of Florida; Estados Unidos
Fil: Kleiman, V.. University of Florida; Estados Unidos
Fil: Tretiak, Sergei. Center for Integrated Nanotechnologies; Estados Unidos
Fil: Fernández Alberti, Sebastián. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
description Photoexcitation of multichromophoric light harvesting molecules induces a number of intramolecular electronic energy relaxation and redistribution pathways that can ultimately lead to ultrafast exciton self-trapping on a single chromophore unit. We investigate the photoinduced processes that take place on a phenylene-ethynylene dendrimer, consisting of nine equivalent linear chromophore units or branches. meta-Substituted links between branches break the conjugation giving rise to weak couplings between them and to localized excitations. Our nonadiabatic excited-state molecular dynamics simulations reveal that the ultrafast internal conversion process to the lowest excited state is accompanied by an inner → outer inter-branch migration of the exciton due to the entropic bias associated with energetically equivalent conjugated segments. The electronic energy redistribution among chromophore units occurs through several possible pathways in which through-bond transport and through-space exciton hopping mechanisms can be distinguished. Besides, triple bond excitations coincide with the localization of the electronic transition densities, suggesting that the intramolecular energy redistribution is a concerted electronic and vibrational energy transfer process.
publishDate 2018
dc.date.none.fl_str_mv 2018-11
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/11336/98342
Ondarse Alvarez, Dianelys; Oldani, Andres Nicolas; Roitberg, A. E.; Kleiman, V.; Tretiak, Sergei; et al.; Energy transfer and spatial scrambling of an exciton in a conjugated dendrimer; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 20; 47; 11-2018; 29648-29660
1463-9076
CONICET Digital
CONICET
url http://hdl.handle.net/11336/98342
identifier_str_mv Ondarse Alvarez, Dianelys; Oldani, Andres Nicolas; Roitberg, A. E.; Kleiman, V.; Tretiak, Sergei; et al.; Energy transfer and spatial scrambling of an exciton in a conjugated dendrimer; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 20; 47; 11-2018; 29648-29660
1463-9076
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2018/CP/C8CP05852K#!divAbstract
info:eu-repo/semantics/altIdentifier/doi/10.1039/c8cp05852k
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 Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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_ 1842269656314806272
score 13.13397

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