Let Digons be Bygones: The Fate of Excitons in Curved π-Systems

Autores
Ondarse Alvarez, Dianelys; Nelson, Tammie; Lupton, John M.; Tretiak, Sergei; Fernández Alberti, Sebastián
Año de publicación
2018
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We explore the diverse origins of unpolarized absorption and emission of molecular polygons consisting of π-conjugated oligomer chains held in a bent geometry by strain controlled at the vertex units. For this purpose, we make use of atomistic nonadiabatic excited-state molecular dynamics simulations of a bichromophore molecular polygon (digon) with bent chromophore chains. Both structural and photoexcited dynamics were found to affect polarization features. Bending strain induces exciton localization on individual chromophore units of the conjugated chains. The latter display different transition dipole moment orientations, a feature not present in the linear oligomer counterparts. In addition, bending makes exciton localization very sensitive to molecular distortions induced by thermal fluctuations. The excited-state dynamics reveals an ultrafast intramolecular energy redistribution that spreads the exciton equally among spatially separated chromophore fragments within the molecular system. As a result, digons become virtually unpolarized absorbers and emitters, in agreement with recent experimental studies on the single-molecule level.
Fil: Ondarse Alvarez, Dianelys.
Fil: Nelson, Tammie.
Fil: Lupton, John M..
Fil: Tretiak, Sergei.
Fil: Fernandez-Alberti, Sebastian.
Materia
NAESMD
MOLECULAR DYNAMICS
MOLECULAR POLYGONS
SURFACE HOPPING
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:11336/92734
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/92734
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Let Digons be Bygones: The Fate of Excitons in Curved π-SystemsOndarse Alvarez, DianelysNelson, TammieLupton, John M.Tretiak, SergeiFernández Alberti, SebastiánNAESMDMOLECULAR DYNAMICSMOLECULAR POLYGONSSURFACE HOPPINGhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1https://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We explore the diverse origins of unpolarized absorption and emission of molecular polygons consisting of π-conjugated oligomer chains held in a bent geometry by strain controlled at the vertex units. For this purpose, we make use of atomistic nonadiabatic excited-state molecular dynamics simulations of a bichromophore molecular polygon (digon) with bent chromophore chains. Both structural and photoexcited dynamics were found to affect polarization features. Bending strain induces exciton localization on individual chromophore units of the conjugated chains. The latter display different transition dipole moment orientations, a feature not present in the linear oligomer counterparts. In addition, bending makes exciton localization very sensitive to molecular distortions induced by thermal fluctuations. The excited-state dynamics reveals an ultrafast intramolecular energy redistribution that spreads the exciton equally among spatially separated chromophore fragments within the molecular system. As a result, digons become virtually unpolarized absorbers and emitters, in agreement with recent experimental studies on the single-molecule level.Fil: Ondarse Alvarez, Dianelys.Fil: Nelson, Tammie.Fil: Lupton, John M..Fil: Tretiak, Sergei.Fil: Fernandez-Alberti, Sebastian.American Chemical Society2018-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/92734Ondarse Alvarez, Dianelys; Nelson, Tammie; Lupton, John M.; Tretiak, Sergei; Fernández Alberti, Sebastián; Let Digons be Bygones: The Fate of Excitons in Curved π-Systems; American Chemical Society; Journal of Physical Chemistry Letters; 9; 24; 12-2018; 7123-71291948-7185CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpclett.8b03160info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpclett.8b03160info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T12:07:18Zoai:ri.conicet.gov.ar:11336/92734instacron: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 12:07:19.133CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Let Digons be Bygones: The Fate of Excitons in Curved π-Systems
title Let Digons be Bygones: The Fate of Excitons in Curved π-Systems
spellingShingle Let Digons be Bygones: The Fate of Excitons in Curved π-Systems
Ondarse Alvarez, Dianelys
NAESMD
MOLECULAR DYNAMICS
MOLECULAR POLYGONS
SURFACE HOPPING
title_short Let Digons be Bygones: The Fate of Excitons in Curved π-Systems
title_full Let Digons be Bygones: The Fate of Excitons in Curved π-Systems
title_fullStr Let Digons be Bygones: The Fate of Excitons in Curved π-Systems
title_full_unstemmed Let Digons be Bygones: The Fate of Excitons in Curved π-Systems
title_sort Let Digons be Bygones: The Fate of Excitons in Curved π-Systems
dc.creator.none.fl_str_mv Ondarse Alvarez, Dianelys
Nelson, Tammie
Lupton, John M.
Tretiak, Sergei
Fernández Alberti, Sebastián
author Ondarse Alvarez, Dianelys
author_facet Ondarse Alvarez, Dianelys
Nelson, Tammie
Lupton, John M.
Tretiak, Sergei
Fernández Alberti, Sebastián
author_role author
author2 Nelson, Tammie
Lupton, John M.
Tretiak, Sergei
Fernández Alberti, Sebastián
author2_role author
author
author
author
dc.subject.none.fl_str_mv NAESMD
MOLECULAR DYNAMICS
MOLECULAR POLYGONS
SURFACE HOPPING
topic NAESMD
MOLECULAR DYNAMICS
MOLECULAR POLYGONS
SURFACE HOPPING
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We explore the diverse origins of unpolarized absorption and emission of molecular polygons consisting of π-conjugated oligomer chains held in a bent geometry by strain controlled at the vertex units. For this purpose, we make use of atomistic nonadiabatic excited-state molecular dynamics simulations of a bichromophore molecular polygon (digon) with bent chromophore chains. Both structural and photoexcited dynamics were found to affect polarization features. Bending strain induces exciton localization on individual chromophore units of the conjugated chains. The latter display different transition dipole moment orientations, a feature not present in the linear oligomer counterparts. In addition, bending makes exciton localization very sensitive to molecular distortions induced by thermal fluctuations. The excited-state dynamics reveals an ultrafast intramolecular energy redistribution that spreads the exciton equally among spatially separated chromophore fragments within the molecular system. As a result, digons become virtually unpolarized absorbers and emitters, in agreement with recent experimental studies on the single-molecule level.
Fil: Ondarse Alvarez, Dianelys.
Fil: Nelson, Tammie.
Fil: Lupton, John M..
Fil: Tretiak, Sergei.
Fil: Fernandez-Alberti, Sebastian.
description We explore the diverse origins of unpolarized absorption and emission of molecular polygons consisting of π-conjugated oligomer chains held in a bent geometry by strain controlled at the vertex units. For this purpose, we make use of atomistic nonadiabatic excited-state molecular dynamics simulations of a bichromophore molecular polygon (digon) with bent chromophore chains. Both structural and photoexcited dynamics were found to affect polarization features. Bending strain induces exciton localization on individual chromophore units of the conjugated chains. The latter display different transition dipole moment orientations, a feature not present in the linear oligomer counterparts. In addition, bending makes exciton localization very sensitive to molecular distortions induced by thermal fluctuations. The excited-state dynamics reveals an ultrafast intramolecular energy redistribution that spreads the exciton equally among spatially separated chromophore fragments within the molecular system. As a result, digons become virtually unpolarized absorbers and emitters, in agreement with recent experimental studies on the single-molecule level.
publishDate 2018
dc.date.none.fl_str_mv 2018-12
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/11336/92734
Ondarse Alvarez, Dianelys; Nelson, Tammie; Lupton, John M.; Tretiak, Sergei; Fernández Alberti, Sebastián; Let Digons be Bygones: The Fate of Excitons in Curved π-Systems; American Chemical Society; Journal of Physical Chemistry Letters; 9; 24; 12-2018; 7123-7129
1948-7185
CONICET Digital
CONICET
url http://hdl.handle.net/11336/92734
identifier_str_mv Ondarse Alvarez, Dianelys; Nelson, Tammie; Lupton, John M.; Tretiak, Sergei; Fernández Alberti, Sebastián; Let Digons be Bygones: The Fate of Excitons in Curved π-Systems; American Chemical Society; Journal of Physical Chemistry Letters; 9; 24; 12-2018; 7123-7129
1948-7185
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/10.1021/acs.jpclett.8b03160
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpclett.8b03160
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 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
_version_ 1846782436898242560
score 12.982451

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