Non-radiative relaxation of photoexcited chlorophylls: Theoretical and experimental study

Autores
Bricker, William P.; Shenai, Prathamesh M.; Ghosh, Avishek; Liu, Zhengtang; Enriquez, Miriam Grace M.; Lambrev, Petar H.; Tan, Howe-Siang; Lo, Cynthia S.; Tretiak, Sergei; Fernández Alberti, Sebastián; Zhao, Yang
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Nonradiative relaxation of high-energy excited states to the lowest excited state in chlorophylls marks the first step in the process of photosynthesis. We perform ultrafast transient absorption spectroscopy measurements, that reveal this internal conversion dynamics to be slightly slower in chlorophyll B than in chlorophyll A. Modeling this process with non -Adiabatic excited state molecular dynamics simulations uncovers a critical role played by the different side groups in the two molecules in governing the intramolecular redistribution of excited state wavefunction, leading, in turn, to different time-scales. Even given smaller electron-vibrational couplings compared to common organic conjugated chromophores, these molecules are able to efficiently dissipate about 1 eV of electronic energy into heat on the timescale of around 200 fs. This is achieved via selective participation of specific atomic groups and complex global migration of the wavefunction from the outer to inner ring, which may have important implications for biological light-harvesting function.
Fil: Bricker, William P.. University of Washington; Estados Unidos
Fil: Shenai, Prathamesh M.. Nanyang Technological University; Singapur
Fil: Ghosh, Avishek. Nanyang Technological University; Singapur
Fil: Liu, Zhengtang. Nanyang Technological University; Singapur
Fil: Enriquez, Miriam Grace M.. Nanyang Technological University; Singapur
Fil: Lambrev, Petar H.. Nanyang Technological University; Singapur. Hungarian Academy of Sciences; Hungría
Fil: Tan, Howe-Siang. Nanyang Technological University; Singapur
Fil: Lo, Cynthia S.. Nanyang Technological University; Singapur
Fil: Tretiak, Sergei. Los Alamos National Laboratory; Estados Unidos
Fil: Fernández Alberti, Sebastián. Universidad Nacional de Quilmes; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Zhao, Yang. Nanyang Technological University; Singapur
Materia
Chlorophylls
Internal conversion
Non-adiabatic molecular dynamics
Excited 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:11336/59282
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/59282
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Non-radiative relaxation of photoexcited chlorophylls: Theoretical and experimental studyBricker, William P.Shenai, Prathamesh M.Ghosh, AvishekLiu, ZhengtangEnriquez, Miriam Grace M.Lambrev, Petar H.Tan, Howe-SiangLo, Cynthia S.Tretiak, SergeiFernández Alberti, SebastiánZhao, YangChlorophyllsInternal conversionNon-adiabatic molecular dynamicsExcited stateshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Nonradiative relaxation of high-energy excited states to the lowest excited state in chlorophylls marks the first step in the process of photosynthesis. We perform ultrafast transient absorption spectroscopy measurements, that reveal this internal conversion dynamics to be slightly slower in chlorophyll B than in chlorophyll A. Modeling this process with non -Adiabatic excited state molecular dynamics simulations uncovers a critical role played by the different side groups in the two molecules in governing the intramolecular redistribution of excited state wavefunction, leading, in turn, to different time-scales. Even given smaller electron-vibrational couplings compared to common organic conjugated chromophores, these molecules are able to efficiently dissipate about 1 eV of electronic energy into heat on the timescale of around 200 fs. This is achieved via selective participation of specific atomic groups and complex global migration of the wavefunction from the outer to inner ring, which may have important implications for biological light-harvesting function.Fil: Bricker, William P.. University of Washington; Estados UnidosFil: Shenai, Prathamesh M.. Nanyang Technological University; SingapurFil: Ghosh, Avishek. Nanyang Technological University; SingapurFil: Liu, Zhengtang. Nanyang Technological University; SingapurFil: Enriquez, Miriam Grace M.. Nanyang Technological University; SingapurFil: Lambrev, Petar H.. Nanyang Technological University; Singapur. Hungarian Academy of Sciences; HungríaFil: Tan, Howe-Siang. Nanyang Technological University; SingapurFil: Lo, Cynthia S.. Nanyang Technological University; SingapurFil: Tretiak, Sergei. Los Alamos National Laboratory; Estados UnidosFil: Fernández Alberti, Sebastián. Universidad Nacional de Quilmes; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Zhao, Yang. Nanyang Technological University; SingapurNature Publishing Group2015-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/59282Bricker, William P.; Shenai, Prathamesh M.; Ghosh, Avishek; Liu, Zhengtang; Enriquez, Miriam Grace M.; et al.; Non-radiative relaxation of photoexcited chlorophylls: Theoretical and experimental study; Nature Publishing Group; Scientific Reports; 5; 9-2015; 13625-136412045-2322CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1038/srep13625info:eu-repo/semantics/altIdentifier/url/https://www.nature.com/articles/srep13625info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:40:17Zoai:ri.conicet.gov.ar:11336/59282instacron: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 11:40:18.265CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Non-radiative relaxation of photoexcited chlorophylls: Theoretical and experimental study
title Non-radiative relaxation of photoexcited chlorophylls: Theoretical and experimental study
spellingShingle Non-radiative relaxation of photoexcited chlorophylls: Theoretical and experimental study
Bricker, William P.
Chlorophylls
Internal conversion
Non-adiabatic molecular dynamics
Excited states
title_short Non-radiative relaxation of photoexcited chlorophylls: Theoretical and experimental study
title_full Non-radiative relaxation of photoexcited chlorophylls: Theoretical and experimental study
title_fullStr Non-radiative relaxation of photoexcited chlorophylls: Theoretical and experimental study
title_full_unstemmed Non-radiative relaxation of photoexcited chlorophylls: Theoretical and experimental study
title_sort Non-radiative relaxation of photoexcited chlorophylls: Theoretical and experimental study
dc.creator.none.fl_str_mv Bricker, William P.
Shenai, Prathamesh M.
Ghosh, Avishek
Liu, Zhengtang
Enriquez, Miriam Grace M.
Lambrev, Petar H.
Tan, Howe-Siang
Lo, Cynthia S.
Tretiak, Sergei
Fernández Alberti, Sebastián
Zhao, Yang
author Bricker, William P.
author_facet Bricker, William P.
Shenai, Prathamesh M.
Ghosh, Avishek
Liu, Zhengtang
Enriquez, Miriam Grace M.
Lambrev, Petar H.
Tan, Howe-Siang
Lo, Cynthia S.
Tretiak, Sergei
Fernández Alberti, Sebastián
Zhao, Yang
author_role author
author2 Shenai, Prathamesh M.
Ghosh, Avishek
Liu, Zhengtang
Enriquez, Miriam Grace M.
Lambrev, Petar H.
Tan, Howe-Siang
Lo, Cynthia S.
Tretiak, Sergei
Fernández Alberti, Sebastián
Zhao, Yang
author2_role author
author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Chlorophylls
Internal conversion
Non-adiabatic molecular dynamics
Excited states
topic Chlorophylls
Internal conversion
Non-adiabatic molecular dynamics
Excited 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 Nonradiative relaxation of high-energy excited states to the lowest excited state in chlorophylls marks the first step in the process of photosynthesis. We perform ultrafast transient absorption spectroscopy measurements, that reveal this internal conversion dynamics to be slightly slower in chlorophyll B than in chlorophyll A. Modeling this process with non -Adiabatic excited state molecular dynamics simulations uncovers a critical role played by the different side groups in the two molecules in governing the intramolecular redistribution of excited state wavefunction, leading, in turn, to different time-scales. Even given smaller electron-vibrational couplings compared to common organic conjugated chromophores, these molecules are able to efficiently dissipate about 1 eV of electronic energy into heat on the timescale of around 200 fs. This is achieved via selective participation of specific atomic groups and complex global migration of the wavefunction from the outer to inner ring, which may have important implications for biological light-harvesting function.
Fil: Bricker, William P.. University of Washington; Estados Unidos
Fil: Shenai, Prathamesh M.. Nanyang Technological University; Singapur
Fil: Ghosh, Avishek. Nanyang Technological University; Singapur
Fil: Liu, Zhengtang. Nanyang Technological University; Singapur
Fil: Enriquez, Miriam Grace M.. Nanyang Technological University; Singapur
Fil: Lambrev, Petar H.. Nanyang Technological University; Singapur. Hungarian Academy of Sciences; Hungría
Fil: Tan, Howe-Siang. Nanyang Technological University; Singapur
Fil: Lo, Cynthia S.. Nanyang Technological University; Singapur
Fil: Tretiak, Sergei. Los Alamos National Laboratory; Estados Unidos
Fil: Fernández Alberti, Sebastián. Universidad Nacional de Quilmes; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Zhao, Yang. Nanyang Technological University; Singapur
description Nonradiative relaxation of high-energy excited states to the lowest excited state in chlorophylls marks the first step in the process of photosynthesis. We perform ultrafast transient absorption spectroscopy measurements, that reveal this internal conversion dynamics to be slightly slower in chlorophyll B than in chlorophyll A. Modeling this process with non -Adiabatic excited state molecular dynamics simulations uncovers a critical role played by the different side groups in the two molecules in governing the intramolecular redistribution of excited state wavefunction, leading, in turn, to different time-scales. Even given smaller electron-vibrational couplings compared to common organic conjugated chromophores, these molecules are able to efficiently dissipate about 1 eV of electronic energy into heat on the timescale of around 200 fs. This is achieved via selective participation of specific atomic groups and complex global migration of the wavefunction from the outer to inner ring, which may have important implications for biological light-harvesting function.
publishDate 2015
dc.date.none.fl_str_mv 2015-09
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/11336/59282
Bricker, William P.; Shenai, Prathamesh M.; Ghosh, Avishek; Liu, Zhengtang; Enriquez, Miriam Grace M.; et al.; Non-radiative relaxation of photoexcited chlorophylls: Theoretical and experimental study; Nature Publishing Group; Scientific Reports; 5; 9-2015; 13625-13641
2045-2322
CONICET Digital
CONICET
url http://hdl.handle.net/11336/59282
identifier_str_mv Bricker, William P.; Shenai, Prathamesh M.; Ghosh, Avishek; Liu, Zhengtang; Enriquez, Miriam Grace M.; et al.; Non-radiative relaxation of photoexcited chlorophylls: Theoretical and experimental study; Nature Publishing Group; Scientific Reports; 5; 9-2015; 13625-13641
2045-2322
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1038/srep13625
info:eu-repo/semantics/altIdentifier/url/https://www.nature.com/articles/srep13625
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 Nature Publishing Group
publisher.none.fl_str_mv Nature Publishing Group
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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