Photoinduced non-adiabatic energy transfer pathways in dendrimer building blocks

Autores
Freixas Lemus, Victor Manuel; Ondarse Alvarez, Dianelys; Tretiak, Sergei; Makhov, D.V.; D. V. Shalashilin; Fernández Alberti, Sebastián
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The efficiency of the intramolecular energy transfer in light harvesting dendrimers is determined by their well-defined architecture with high degree of order. After photoexcitation, through-space and through-bond energy transfer mechanisms can take place, involving vectorial exciton migration among different chromophores within dendrimer highly branched structures. Their inherent intramolecular energy gradient depends on how the multiple chromophoric units have been assembled, subject to their inter-connects, spatial distances, and orientations. Herein, we compare the photoinduced nonadiabatic molecular dynamics simulations performed on a set of different combinations of a chain of linked dendrimer building blocks composed of two-, three-, and four-ring linear polyphenylene chromophoric units. The calculations are performed with the recently developed ab initio multiple cloning-time dependent diabatic basis implementation of the Multiconfigurational Ehrenfest (MCE) approach. Despite differences in short time relaxation pathways and different initial exciton localization, at longer time scales, electronic relaxation rates and exciton final redistributions are very similar for all combinations. Unlike the systems composed of two building blocks, considered previously, for the larger 3 block systems here we observe that bifurcation of the wave function accounted by cloning is important. In all the systems considered in this work, at the time scale of few hundreds of femtoseconds, cloning enhances the electronic energy relaxation by ∼13% compared to that of the MCE method without cloning. Thus, accurate description of quantum effects is essential for understanding of the energy exchange in dendrimers both at short and long time scales.
Fil: Freixas Lemus, Victor Manuel. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Ondarse Alvarez, Dianelys. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina
Fil: Tretiak, Sergei. Los Alamos National Laboratory; Estados Unidos
Fil: Makhov, D.V.. University Of Leeds; Reino Unido
Fil: D. V. Shalashilin. University Of Leeds; Reino Unido
Fil: Fernández Alberti, Sebastián. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Materia
DYNAMICS
EHRENFEST
CLONING
POLYMERS
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:11336/118322
Acceder
id CONICETDig_758e940d359fdec87d431593b7fe6e32
oai_identifier_str oai:ri.conicet.gov.ar:11336/118322
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Photoinduced non-adiabatic energy transfer pathways in dendrimer building blocksFreixas Lemus, Victor ManuelOndarse Alvarez, DianelysTretiak, SergeiMakhov, D.V.D. V. ShalashilinFernández Alberti, SebastiánDYNAMICSEHRENFESTCLONINGPOLYMERShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The efficiency of the intramolecular energy transfer in light harvesting dendrimers is determined by their well-defined architecture with high degree of order. After photoexcitation, through-space and through-bond energy transfer mechanisms can take place, involving vectorial exciton migration among different chromophores within dendrimer highly branched structures. Their inherent intramolecular energy gradient depends on how the multiple chromophoric units have been assembled, subject to their inter-connects, spatial distances, and orientations. Herein, we compare the photoinduced nonadiabatic molecular dynamics simulations performed on a set of different combinations of a chain of linked dendrimer building blocks composed of two-, three-, and four-ring linear polyphenylene chromophoric units. The calculations are performed with the recently developed ab initio multiple cloning-time dependent diabatic basis implementation of the Multiconfigurational Ehrenfest (MCE) approach. Despite differences in short time relaxation pathways and different initial exciton localization, at longer time scales, electronic relaxation rates and exciton final redistributions are very similar for all combinations. Unlike the systems composed of two building blocks, considered previously, for the larger 3 block systems here we observe that bifurcation of the wave function accounted by cloning is important. In all the systems considered in this work, at the time scale of few hundreds of femtoseconds, cloning enhances the electronic energy relaxation by ∼13% compared to that of the MCE method without cloning. Thus, accurate description of quantum effects is essential for understanding of the energy exchange in dendrimers both at short and long time scales.Fil: Freixas Lemus, Victor Manuel. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Ondarse Alvarez, Dianelys. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; ArgentinaFil: Tretiak, Sergei. Los Alamos National Laboratory; Estados UnidosFil: Makhov, D.V.. University Of Leeds; Reino UnidoFil: D. V. Shalashilin. University Of Leeds; Reino UnidoFil: Fernández Alberti, Sebastián. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaAmerican Institute of Physics2019-03info: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/11336/118322Freixas Lemus, Victor Manuel; Ondarse Alvarez, Dianelys; Tretiak, Sergei; Makhov, D.V.; D. V. Shalashilin; et al.; Photoinduced non-adiabatic energy transfer pathways in dendrimer building blocks; American Institute of Physics; Journal of Chemical Physics; 150; 12; 3-2019; 1-110021-9606CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://aip.scitation.org/doi/10.1063/1.5086680info:eu-repo/semantics/altIdentifier/doi/10.1063/1.5086680info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:10:38Zoai:ri.conicet.gov.ar:11336/118322instacron: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 10:10:38.817CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Photoinduced non-adiabatic energy transfer pathways in dendrimer building blocks
title Photoinduced non-adiabatic energy transfer pathways in dendrimer building blocks
spellingShingle Photoinduced non-adiabatic energy transfer pathways in dendrimer building blocks
Freixas Lemus, Victor Manuel
DYNAMICS
EHRENFEST
CLONING
POLYMERS
title_short Photoinduced non-adiabatic energy transfer pathways in dendrimer building blocks
title_full Photoinduced non-adiabatic energy transfer pathways in dendrimer building blocks
title_fullStr Photoinduced non-adiabatic energy transfer pathways in dendrimer building blocks
title_full_unstemmed Photoinduced non-adiabatic energy transfer pathways in dendrimer building blocks
title_sort Photoinduced non-adiabatic energy transfer pathways in dendrimer building blocks
dc.creator.none.fl_str_mv Freixas Lemus, Victor Manuel
Ondarse Alvarez, Dianelys
Tretiak, Sergei
Makhov, D.V.
D. V. Shalashilin
Fernández Alberti, Sebastián
author Freixas Lemus, Victor Manuel
author_facet Freixas Lemus, Victor Manuel
Ondarse Alvarez, Dianelys
Tretiak, Sergei
Makhov, D.V.
D. V. Shalashilin
Fernández Alberti, Sebastián
author_role author
author2 Ondarse Alvarez, Dianelys
Tretiak, Sergei
Makhov, D.V.
D. V. Shalashilin
Fernández Alberti, Sebastián
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv DYNAMICS
EHRENFEST
CLONING
POLYMERS
topic DYNAMICS
EHRENFEST
CLONING
POLYMERS
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 efficiency of the intramolecular energy transfer in light harvesting dendrimers is determined by their well-defined architecture with high degree of order. After photoexcitation, through-space and through-bond energy transfer mechanisms can take place, involving vectorial exciton migration among different chromophores within dendrimer highly branched structures. Their inherent intramolecular energy gradient depends on how the multiple chromophoric units have been assembled, subject to their inter-connects, spatial distances, and orientations. Herein, we compare the photoinduced nonadiabatic molecular dynamics simulations performed on a set of different combinations of a chain of linked dendrimer building blocks composed of two-, three-, and four-ring linear polyphenylene chromophoric units. The calculations are performed with the recently developed ab initio multiple cloning-time dependent diabatic basis implementation of the Multiconfigurational Ehrenfest (MCE) approach. Despite differences in short time relaxation pathways and different initial exciton localization, at longer time scales, electronic relaxation rates and exciton final redistributions are very similar for all combinations. Unlike the systems composed of two building blocks, considered previously, for the larger 3 block systems here we observe that bifurcation of the wave function accounted by cloning is important. In all the systems considered in this work, at the time scale of few hundreds of femtoseconds, cloning enhances the electronic energy relaxation by ∼13% compared to that of the MCE method without cloning. Thus, accurate description of quantum effects is essential for understanding of the energy exchange in dendrimers both at short and long time scales.
Fil: Freixas Lemus, Victor Manuel. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Ondarse Alvarez, Dianelys. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina
Fil: Tretiak, Sergei. Los Alamos National Laboratory; Estados Unidos
Fil: Makhov, D.V.. University Of Leeds; Reino Unido
Fil: D. V. Shalashilin. University Of Leeds; Reino Unido
Fil: Fernández Alberti, Sebastián. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
description The efficiency of the intramolecular energy transfer in light harvesting dendrimers is determined by their well-defined architecture with high degree of order. After photoexcitation, through-space and through-bond energy transfer mechanisms can take place, involving vectorial exciton migration among different chromophores within dendrimer highly branched structures. Their inherent intramolecular energy gradient depends on how the multiple chromophoric units have been assembled, subject to their inter-connects, spatial distances, and orientations. Herein, we compare the photoinduced nonadiabatic molecular dynamics simulations performed on a set of different combinations of a chain of linked dendrimer building blocks composed of two-, three-, and four-ring linear polyphenylene chromophoric units. The calculations are performed with the recently developed ab initio multiple cloning-time dependent diabatic basis implementation of the Multiconfigurational Ehrenfest (MCE) approach. Despite differences in short time relaxation pathways and different initial exciton localization, at longer time scales, electronic relaxation rates and exciton final redistributions are very similar for all combinations. Unlike the systems composed of two building blocks, considered previously, for the larger 3 block systems here we observe that bifurcation of the wave function accounted by cloning is important. In all the systems considered in this work, at the time scale of few hundreds of femtoseconds, cloning enhances the electronic energy relaxation by ∼13% compared to that of the MCE method without cloning. Thus, accurate description of quantum effects is essential for understanding of the energy exchange in dendrimers both at short and long time scales.
publishDate 2019
dc.date.none.fl_str_mv 2019-03
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/11336/118322
Freixas Lemus, Victor Manuel; Ondarse Alvarez, Dianelys; Tretiak, Sergei; Makhov, D.V.; D. V. Shalashilin; et al.; Photoinduced non-adiabatic energy transfer pathways in dendrimer building blocks; American Institute of Physics; Journal of Chemical Physics; 150; 12; 3-2019; 1-11
0021-9606
CONICET Digital
CONICET
url http://hdl.handle.net/11336/118322
identifier_str_mv Freixas Lemus, Victor Manuel; Ondarse Alvarez, Dianelys; Tretiak, Sergei; Makhov, D.V.; D. V. Shalashilin; et al.; Photoinduced non-adiabatic energy transfer pathways in dendrimer building blocks; American Institute of Physics; Journal of Chemical Physics; 150; 12; 3-2019; 1-11
0021-9606
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://aip.scitation.org/doi/10.1063/1.5086680
info:eu-repo/semantics/altIdentifier/doi/10.1063/1.5086680
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 Institute of Physics
publisher.none.fl_str_mv American Institute of Physics
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 13.13397

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