Computational study of photoexcited dynamics in bichromophoric cross-shaped oligofluorene

Autores
Ondarse Alvarez, Dianelys; Oldani, Andres Nicolas; Tretiak, S.; Fernández Alberti, Sebastián
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The non-adiabatic excited state molecular dynamics (NA-ESMD) approach is applied to investigate photoexcited dynamics and relaxation pathways in a spiro-linked conjugated polyfluorene at room (T = 300 K) and low (T = 10 K) temperatures. This dimeric aggregate consists of two perpendicularly oriented weakly interacting α-polyfluorene oligomers. The negligible coupling between the monomer chains results in an initial absorption band composed of equal contributions of the two lowest excited electronic states, each localized on one of the two chains. After photoexcitation, an efficient ultrafast localization of the entire electronic population to the lowest excited state is observed on the time scale of about 100 fs. Both internal conversion between excited electronic states and vibronic energy relaxation on a single electronic state contribute to this process. Thus, photoexcited dynamics of the polyfluorene dimer follows two distinct pathways with substantial temperature dependence on their efficiency. One relaxation channel involves resonance electronic energy transfer between the monomer chains, whereas the second pathway concerns the relaxation of the electronic energy on the same chain that has been initially excited due to electron-phonon coupling. Despite the slower vibrational relaxation, a more efficient ultrafast electronic relaxation is observed at low temperature. Our numerical simulations analyze the effects of molecular geometry distortion during the electronic energy redistribution and suggest spectroscopic signatures reflecting complex electron-vibrational dynamics.
Fil: Ondarse Alvarez, Dianelys. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes; Argentina
Fil: Oldani, Andres Nicolas. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes; Argentina
Fil: Tretiak, S.. Los Alamos National Laboratory. Los Alamos; Estados Unidos
Fil: Fernández Alberti, Sebastián. Universidad Nacional de Quilmes; Argentina
Materia
Dendrímeros
Dinámica
Ceo
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acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
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Consejo Nacional de Investigaciones Científicas y Técnicas
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oai:ri.conicet.gov.ar:11336/36539
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Computational study of photoexcited dynamics in bichromophoric cross-shaped oligofluoreneOndarse Alvarez, DianelysOldani, Andres NicolasTretiak, S.Fernández Alberti, SebastiánDendrímerosDinámicaCeohttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The non-adiabatic excited state molecular dynamics (NA-ESMD) approach is applied to investigate photoexcited dynamics and relaxation pathways in a spiro-linked conjugated polyfluorene at room (T = 300 K) and low (T = 10 K) temperatures. This dimeric aggregate consists of two perpendicularly oriented weakly interacting α-polyfluorene oligomers. The negligible coupling between the monomer chains results in an initial absorption band composed of equal contributions of the two lowest excited electronic states, each localized on one of the two chains. After photoexcitation, an efficient ultrafast localization of the entire electronic population to the lowest excited state is observed on the time scale of about 100 fs. Both internal conversion between excited electronic states and vibronic energy relaxation on a single electronic state contribute to this process. Thus, photoexcited dynamics of the polyfluorene dimer follows two distinct pathways with substantial temperature dependence on their efficiency. One relaxation channel involves resonance electronic energy transfer between the monomer chains, whereas the second pathway concerns the relaxation of the electronic energy on the same chain that has been initially excited due to electron-phonon coupling. Despite the slower vibrational relaxation, a more efficient ultrafast electronic relaxation is observed at low temperature. Our numerical simulations analyze the effects of molecular geometry distortion during the electronic energy redistribution and suggest spectroscopic signatures reflecting complex electron-vibrational dynamics.Fil: Ondarse Alvarez, Dianelys. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes; ArgentinaFil: Oldani, Andres Nicolas. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes; ArgentinaFil: Tretiak, S.. Los Alamos National Laboratory. Los Alamos; Estados UnidosFil: Fernández Alberti, Sebastián. Universidad Nacional de Quilmes; ArgentinaAmerican Chemical Society2014-11info: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/11336/36539Ondarse Alvarez, Dianelys; Oldani, Andres Nicolas; Tretiak, S.; Fernández Alberti, Sebastián; Computational study of photoexcited dynamics in bichromophoric cross-shaped oligofluorene; American Chemical Society; Journal of Physical Chemistry A; 118; 45; 11-2014; 10742-107531089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/jp504720ninfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp504720ninfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-11-12T09:46:52Zoai:ri.conicet.gov.ar:11336/36539instacron: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:34982025-11-12 09:46:53.106CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Computational study of photoexcited dynamics in bichromophoric cross-shaped oligofluorene
title Computational study of photoexcited dynamics in bichromophoric cross-shaped oligofluorene
spellingShingle Computational study of photoexcited dynamics in bichromophoric cross-shaped oligofluorene
Ondarse Alvarez, Dianelys
Dendrímeros
Dinámica
Ceo
title_short Computational study of photoexcited dynamics in bichromophoric cross-shaped oligofluorene
title_full Computational study of photoexcited dynamics in bichromophoric cross-shaped oligofluorene
title_fullStr Computational study of photoexcited dynamics in bichromophoric cross-shaped oligofluorene
title_full_unstemmed Computational study of photoexcited dynamics in bichromophoric cross-shaped oligofluorene
title_sort Computational study of photoexcited dynamics in bichromophoric cross-shaped oligofluorene
dc.creator.none.fl_str_mv Ondarse Alvarez, Dianelys
Oldani, Andres Nicolas
Tretiak, S.
Fernández Alberti, Sebastián
author Ondarse Alvarez, Dianelys
author_facet Ondarse Alvarez, Dianelys
Oldani, Andres Nicolas
Tretiak, S.
Fernández Alberti, Sebastián
author_role author
author2 Oldani, Andres Nicolas
Tretiak, S.
Fernández Alberti, Sebastián
author2_role author
author
author
dc.subject.none.fl_str_mv Dendrímeros
Dinámica
Ceo
topic Dendrímeros
Dinámica
Ceo
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The non-adiabatic excited state molecular dynamics (NA-ESMD) approach is applied to investigate photoexcited dynamics and relaxation pathways in a spiro-linked conjugated polyfluorene at room (T = 300 K) and low (T = 10 K) temperatures. This dimeric aggregate consists of two perpendicularly oriented weakly interacting α-polyfluorene oligomers. The negligible coupling between the monomer chains results in an initial absorption band composed of equal contributions of the two lowest excited electronic states, each localized on one of the two chains. After photoexcitation, an efficient ultrafast localization of the entire electronic population to the lowest excited state is observed on the time scale of about 100 fs. Both internal conversion between excited electronic states and vibronic energy relaxation on a single electronic state contribute to this process. Thus, photoexcited dynamics of the polyfluorene dimer follows two distinct pathways with substantial temperature dependence on their efficiency. One relaxation channel involves resonance electronic energy transfer between the monomer chains, whereas the second pathway concerns the relaxation of the electronic energy on the same chain that has been initially excited due to electron-phonon coupling. Despite the slower vibrational relaxation, a more efficient ultrafast electronic relaxation is observed at low temperature. Our numerical simulations analyze the effects of molecular geometry distortion during the electronic energy redistribution and suggest spectroscopic signatures reflecting complex electron-vibrational dynamics.
Fil: Ondarse Alvarez, Dianelys. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes; Argentina
Fil: Oldani, Andres Nicolas. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes; Argentina
Fil: Tretiak, S.. Los Alamos National Laboratory. Los Alamos; Estados Unidos
Fil: Fernández Alberti, Sebastián. Universidad Nacional de Quilmes; Argentina
description The non-adiabatic excited state molecular dynamics (NA-ESMD) approach is applied to investigate photoexcited dynamics and relaxation pathways in a spiro-linked conjugated polyfluorene at room (T = 300 K) and low (T = 10 K) temperatures. This dimeric aggregate consists of two perpendicularly oriented weakly interacting α-polyfluorene oligomers. The negligible coupling between the monomer chains results in an initial absorption band composed of equal contributions of the two lowest excited electronic states, each localized on one of the two chains. After photoexcitation, an efficient ultrafast localization of the entire electronic population to the lowest excited state is observed on the time scale of about 100 fs. Both internal conversion between excited electronic states and vibronic energy relaxation on a single electronic state contribute to this process. Thus, photoexcited dynamics of the polyfluorene dimer follows two distinct pathways with substantial temperature dependence on their efficiency. One relaxation channel involves resonance electronic energy transfer between the monomer chains, whereas the second pathway concerns the relaxation of the electronic energy on the same chain that has been initially excited due to electron-phonon coupling. Despite the slower vibrational relaxation, a more efficient ultrafast electronic relaxation is observed at low temperature. Our numerical simulations analyze the effects of molecular geometry distortion during the electronic energy redistribution and suggest spectroscopic signatures reflecting complex electron-vibrational dynamics.
publishDate 2014
dc.date.none.fl_str_mv 2014-11
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/11336/36539
Ondarse Alvarez, Dianelys; Oldani, Andres Nicolas; Tretiak, S.; Fernández Alberti, Sebastián; Computational study of photoexcited dynamics in bichromophoric cross-shaped oligofluorene; American Chemical Society; Journal of Physical Chemistry A; 118; 45; 11-2014; 10742-10753
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/36539
identifier_str_mv Ondarse Alvarez, Dianelys; Oldani, Andres Nicolas; Tretiak, S.; Fernández Alberti, Sebastián; Computational study of photoexcited dynamics in bichromophoric cross-shaped oligofluorene; American Chemical Society; Journal of Physical Chemistry A; 118; 45; 11-2014; 10742-10753
1089-5639
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.acs.org/doi/abs/10.1021/jp504720n
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp504720n
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 American Chemical Society
publisher.none.fl_str_mv American Chemical 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 13.24909

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