Self-trapping of excitons, violation of condon approximation, and efficient fluorescence in conjugated cycloparaphenylenes

Autores
Adamska, Lyudmyla; Nayyar, Iffat; Chen, Hang; Swan, Anna K.; Oldani, Andres Nicolas; Fernández Alberti, Sebastián; Golder, Matthew R.; Jasti, Ramesh; Doorn, Stephen K.; Tretiak, Sergei
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Cycloparaphenylenes, the simplest structural unit of armchair carbon nanotubes, have unique optoelectronic properties counterintuitive in the class of conjugated organic materials. Our time-dependent density functional theory study and excited state dynamics simulations of cycloparaphenylene chromophores provide a simple and conceptually appealing physical picture explaining experimentally observed trends in optical properties in this family of molecules. Fully delocalized degenerate second and third excitonic states define linear absorption spectra. Self-trapping of the lowest excitonic state due to electron-phonon coupling leads to the formation of spatially localized excitation in large cycloparaphenylenes within 100 fs. This invalidates the commonly used Condon approximation and breaks optical selection rules, making these materials superior fluorophores. This process does not occur in the small molecules, which remain inefficient emitters. A complex interplay of symmetry, π-conjugation, conformational distortion and bending strain controls all photophysics of cycloparaphenylenes.
Fil: Adamska, Lyudmyla. Los Alamos National Laboratory. Los Alamos; Estados Unidos
Fil: Nayyar, Iffat. Los Alamos National Laboratory. Los Alamos; Estados Unidos
Fil: Chen, Hang. Boston University; Estados Unidos
Fil: Swan, Anna K.. Boston University; Estados Unidos
Fil: Oldani, Andres Nicolas. Universidad Nacional de Quilmes; Argentina
Fil: Fernández Alberti, Sebastián. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes; Argentina
Fil: Golder, Matthew R.. University of Oregon; Estados Unidos
Fil: Jasti, Ramesh. University of Oregon; Estados Unidos
Fil: Doorn, Stephen K.. Los Alamos National Laboratory. Los Alamos; Estados Unidos
Fil: Tretiak, Sergei. Los Alamos National Laboratory. Los Alamos; Estados Unidos
Materia
Exciton-Vibrational Coupling
Nonadiabatic Excited State Molecular Dynamics
Photoluminescence Spectra
Time-Dependent Density Functional Theory
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:11336/36541
Acceder
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network_acronym_str CONICETDig
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network_name_str CONICET Digital (CONICET)
spelling Self-trapping of excitons, violation of condon approximation, and efficient fluorescence in conjugated cycloparaphenylenesAdamska, LyudmylaNayyar, IffatChen, HangSwan, Anna K.Oldani, Andres NicolasFernández Alberti, SebastiánGolder, Matthew R.Jasti, RameshDoorn, Stephen K.Tretiak, SergeiExciton-Vibrational CouplingNonadiabatic Excited State Molecular DynamicsPhotoluminescence SpectraTime-Dependent Density Functional Theoryhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Cycloparaphenylenes, the simplest structural unit of armchair carbon nanotubes, have unique optoelectronic properties counterintuitive in the class of conjugated organic materials. Our time-dependent density functional theory study and excited state dynamics simulations of cycloparaphenylene chromophores provide a simple and conceptually appealing physical picture explaining experimentally observed trends in optical properties in this family of molecules. Fully delocalized degenerate second and third excitonic states define linear absorption spectra. Self-trapping of the lowest excitonic state due to electron-phonon coupling leads to the formation of spatially localized excitation in large cycloparaphenylenes within 100 fs. This invalidates the commonly used Condon approximation and breaks optical selection rules, making these materials superior fluorophores. This process does not occur in the small molecules, which remain inefficient emitters. A complex interplay of symmetry, π-conjugation, conformational distortion and bending strain controls all photophysics of cycloparaphenylenes.Fil: Adamska, Lyudmyla. Los Alamos National Laboratory. Los Alamos; Estados UnidosFil: Nayyar, Iffat. Los Alamos National Laboratory. Los Alamos; Estados UnidosFil: Chen, Hang. Boston University; Estados UnidosFil: Swan, Anna K.. Boston University; Estados UnidosFil: Oldani, Andres Nicolas. Universidad Nacional de Quilmes; ArgentinaFil: Fernández Alberti, Sebastián. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes; ArgentinaFil: Golder, Matthew R.. University of Oregon; Estados UnidosFil: Jasti, Ramesh. University of Oregon; Estados UnidosFil: Doorn, Stephen K.. Los Alamos National Laboratory. Los Alamos; Estados UnidosFil: Tretiak, Sergei. Los Alamos National Laboratory. Los Alamos; Estados UnidosAmerican Chemical Society2014-11info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/36541Adamska, Lyudmyla; Nayyar, Iffat; Chen, Hang; Swan, Anna K.; Oldani, Andres Nicolas; et al.; Self-trapping of excitons, violation of condon approximation, and efficient fluorescence in conjugated cycloparaphenylenes; American Chemical Society; Nano Letters; 14; 11; 11-2014; 6539-65461530-6984CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/nl503133einfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:12:26Zoai:ri.conicet.gov.ar:11336/36541instacron: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 11:12:26.912CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Self-trapping of excitons, violation of condon approximation, and efficient fluorescence in conjugated cycloparaphenylenes
title Self-trapping of excitons, violation of condon approximation, and efficient fluorescence in conjugated cycloparaphenylenes
spellingShingle Self-trapping of excitons, violation of condon approximation, and efficient fluorescence in conjugated cycloparaphenylenes
Adamska, Lyudmyla
Exciton-Vibrational Coupling
Nonadiabatic Excited State Molecular Dynamics
Photoluminescence Spectra
Time-Dependent Density Functional Theory
title_short Self-trapping of excitons, violation of condon approximation, and efficient fluorescence in conjugated cycloparaphenylenes
title_full Self-trapping of excitons, violation of condon approximation, and efficient fluorescence in conjugated cycloparaphenylenes
title_fullStr Self-trapping of excitons, violation of condon approximation, and efficient fluorescence in conjugated cycloparaphenylenes
title_full_unstemmed Self-trapping of excitons, violation of condon approximation, and efficient fluorescence in conjugated cycloparaphenylenes
title_sort Self-trapping of excitons, violation of condon approximation, and efficient fluorescence in conjugated cycloparaphenylenes
dc.creator.none.fl_str_mv Adamska, Lyudmyla
Nayyar, Iffat
Chen, Hang
Swan, Anna K.
Oldani, Andres Nicolas
Fernández Alberti, Sebastián
Golder, Matthew R.
Jasti, Ramesh
Doorn, Stephen K.
Tretiak, Sergei
author Adamska, Lyudmyla
author_facet Adamska, Lyudmyla
Nayyar, Iffat
Chen, Hang
Swan, Anna K.
Oldani, Andres Nicolas
Fernández Alberti, Sebastián
Golder, Matthew R.
Jasti, Ramesh
Doorn, Stephen K.
Tretiak, Sergei
author_role author
author2 Nayyar, Iffat
Chen, Hang
Swan, Anna K.
Oldani, Andres Nicolas
Fernández Alberti, Sebastián
Golder, Matthew R.
Jasti, Ramesh
Doorn, Stephen K.
Tretiak, Sergei
author2_role author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Exciton-Vibrational Coupling
Nonadiabatic Excited State Molecular Dynamics
Photoluminescence Spectra
Time-Dependent Density Functional Theory
topic Exciton-Vibrational Coupling
Nonadiabatic Excited State Molecular Dynamics
Photoluminescence Spectra
Time-Dependent Density Functional Theory
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Cycloparaphenylenes, the simplest structural unit of armchair carbon nanotubes, have unique optoelectronic properties counterintuitive in the class of conjugated organic materials. Our time-dependent density functional theory study and excited state dynamics simulations of cycloparaphenylene chromophores provide a simple and conceptually appealing physical picture explaining experimentally observed trends in optical properties in this family of molecules. Fully delocalized degenerate second and third excitonic states define linear absorption spectra. Self-trapping of the lowest excitonic state due to electron-phonon coupling leads to the formation of spatially localized excitation in large cycloparaphenylenes within 100 fs. This invalidates the commonly used Condon approximation and breaks optical selection rules, making these materials superior fluorophores. This process does not occur in the small molecules, which remain inefficient emitters. A complex interplay of symmetry, π-conjugation, conformational distortion and bending strain controls all photophysics of cycloparaphenylenes.
Fil: Adamska, Lyudmyla. Los Alamos National Laboratory. Los Alamos; Estados Unidos
Fil: Nayyar, Iffat. Los Alamos National Laboratory. Los Alamos; Estados Unidos
Fil: Chen, Hang. Boston University; Estados Unidos
Fil: Swan, Anna K.. Boston University; Estados Unidos
Fil: Oldani, Andres Nicolas. Universidad Nacional de Quilmes; Argentina
Fil: Fernández Alberti, Sebastián. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes; Argentina
Fil: Golder, Matthew R.. University of Oregon; Estados Unidos
Fil: Jasti, Ramesh. University of Oregon; Estados Unidos
Fil: Doorn, Stephen K.. Los Alamos National Laboratory. Los Alamos; Estados Unidos
Fil: Tretiak, Sergei. Los Alamos National Laboratory. Los Alamos; Estados Unidos
description Cycloparaphenylenes, the simplest structural unit of armchair carbon nanotubes, have unique optoelectronic properties counterintuitive in the class of conjugated organic materials. Our time-dependent density functional theory study and excited state dynamics simulations of cycloparaphenylene chromophores provide a simple and conceptually appealing physical picture explaining experimentally observed trends in optical properties in this family of molecules. Fully delocalized degenerate second and third excitonic states define linear absorption spectra. Self-trapping of the lowest excitonic state due to electron-phonon coupling leads to the formation of spatially localized excitation in large cycloparaphenylenes within 100 fs. This invalidates the commonly used Condon approximation and breaks optical selection rules, making these materials superior fluorophores. This process does not occur in the small molecules, which remain inefficient emitters. A complex interplay of symmetry, π-conjugation, conformational distortion and bending strain controls all photophysics of cycloparaphenylenes.
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/11336/36541
Adamska, Lyudmyla; Nayyar, Iffat; Chen, Hang; Swan, Anna K.; Oldani, Andres Nicolas; et al.; Self-trapping of excitons, violation of condon approximation, and efficient fluorescence in conjugated cycloparaphenylenes; American Chemical Society; Nano Letters; 14; 11; 11-2014; 6539-6546
1530-6984
CONICET Digital
CONICET
url http://hdl.handle.net/11336/36541
identifier_str_mv Adamska, Lyudmyla; Nayyar, Iffat; Chen, Hang; Swan, Anna K.; Oldani, Andres Nicolas; et al.; Self-trapping of excitons, violation of condon approximation, and efficient fluorescence in conjugated cycloparaphenylenes; American Chemical Society; Nano Letters; 14; 11; 11-2014; 6539-6546
1530-6984
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/nl503133e
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_ 1846781517655703552
score 12.982451

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