Internal Conversion and Vibrational Energy Redistribution in Chlorophyll A

Autores
Shenai, Prathamesh M.; Fernández Alberti, Sebastián; Bricker, William P.; Tretiak, Sergei; Zhao, Yang
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We have computationally investigated the role of intramolecular vibrational modes in determining nonradiative relaxation pathways of photoexcited electronic states in isolated chlorophyll A (ChlA) molecules. To simulate the excited state relaxation from the initially excited Soret state to the lowest excited state Qy, the approach of nonadiabatic excited state molecular dynamics has been adopted. The intramolecular vibrational energy relaxation and redistribution that accompany the electronic internal conversion process is followed by analyzing the excited state trajectories in terms of the ground state equilibrium normal modes. The time dependence of the normal mode velocities is determined by projecting instantaneous Cartesian velocities onto the normal mode vectors. Our analysis of the time evolution of the average mode energies uncovers that only a small subset of the medium-to-high frequency normal modes actively participate in the electronic relaxation processes. These active modes are characterized by the highest overlap with the nonadiabatic coupling vectors(NACRs) during the electronic transitions. Further statistical analysis of the nonadiabatic transitions reveals that the electronic and vibrational energy relaxation occurs via two distinct pathways with significantly different time scales on which the hopping from Soret to Qx occurs thereby dictating the overall dynamics. Furthermore, the NACRs corresponding to each of the transitions have been consistently found to be predominantly similar to a set of normal modes that vary depending upon the transition and the identified categories. Each pathway exhibits a differential time scale of energy transfer and also a differential set of predominant active modes. Our present analysis can be considered as a general approach allowing identification of a reducedsubset of specific vibrational coordinates associated with nonradiative relaxation pathways. Therefore, it represents an adequate prior strategy that can particularly facilitates mixed quantum-classical approaches.
Fil: Shenai, Prathamesh M.. Nanyang Technological University; Singapur
Fil: Fernández Alberti, Sebastián. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes; Argentina
Fil: Bricker, William P.. University of Washington; Estados Unidos
Fil: Tretiak, Sergei. Los Alamos National High Magnetic Field Laboratory; Estados Unidos
Fil: Zhao, Yang. Nanyang Technological University; Singapur
Materia
Vibrational Relaxation
Excited States
Normal Modes
Chlorophylls
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:11336/42354

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network_name_str CONICET Digital (CONICET)
spelling Internal Conversion and Vibrational Energy Redistribution in Chlorophyll AShenai, Prathamesh M.Fernández Alberti, SebastiánBricker, William P.Tretiak, SergeiZhao, YangVibrational RelaxationExcited StatesNormal ModesChlorophyllshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We have computationally investigated the role of intramolecular vibrational modes in determining nonradiative relaxation pathways of photoexcited electronic states in isolated chlorophyll A (ChlA) molecules. To simulate the excited state relaxation from the initially excited Soret state to the lowest excited state Qy, the approach of nonadiabatic excited state molecular dynamics has been adopted. The intramolecular vibrational energy relaxation and redistribution that accompany the electronic internal conversion process is followed by analyzing the excited state trajectories in terms of the ground state equilibrium normal modes. The time dependence of the normal mode velocities is determined by projecting instantaneous Cartesian velocities onto the normal mode vectors. Our analysis of the time evolution of the average mode energies uncovers that only a small subset of the medium-to-high frequency normal modes actively participate in the electronic relaxation processes. These active modes are characterized by the highest overlap with the nonadiabatic coupling vectors(NACRs) during the electronic transitions. Further statistical analysis of the nonadiabatic transitions reveals that the electronic and vibrational energy relaxation occurs via two distinct pathways with significantly different time scales on which the hopping from Soret to Qx occurs thereby dictating the overall dynamics. Furthermore, the NACRs corresponding to each of the transitions have been consistently found to be predominantly similar to a set of normal modes that vary depending upon the transition and the identified categories. Each pathway exhibits a differential time scale of energy transfer and also a differential set of predominant active modes. Our present analysis can be considered as a general approach allowing identification of a reducedsubset of specific vibrational coordinates associated with nonradiative relaxation pathways. Therefore, it represents an adequate prior strategy that can particularly facilitates mixed quantum-classical approaches.Fil: Shenai, Prathamesh M.. Nanyang Technological University; SingapurFil: Fernández Alberti, Sebastián. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes; ArgentinaFil: Bricker, William P.. University of Washington; Estados UnidosFil: Tretiak, Sergei. Los Alamos National High Magnetic Field Laboratory; Estados UnidosFil: Zhao, Yang. Nanyang Technological University; SingapurAmerican Chemical Society2015-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/42354Shenai, Prathamesh M.; Fernández Alberti, Sebastián; Bricker, William P.; Tretiak, Sergei; Zhao, Yang; Internal Conversion and Vibrational Energy Redistribution in Chlorophyll A; American Chemical Society; Journal of Physical Chemistry B; 120; 1; 12-2015; 49-581520-6106CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/acs.jpcb.5b09548info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcb.5b09548info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:46:00Zoai:ri.conicet.gov.ar:11336/42354instacron: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:34982025-09-29 10:46:00.915CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Internal Conversion and Vibrational Energy Redistribution in Chlorophyll A
title Internal Conversion and Vibrational Energy Redistribution in Chlorophyll A
spellingShingle Internal Conversion and Vibrational Energy Redistribution in Chlorophyll A
Shenai, Prathamesh M.
Vibrational Relaxation
Excited States
Normal Modes
Chlorophylls
title_short Internal Conversion and Vibrational Energy Redistribution in Chlorophyll A
title_full Internal Conversion and Vibrational Energy Redistribution in Chlorophyll A
title_fullStr Internal Conversion and Vibrational Energy Redistribution in Chlorophyll A
title_full_unstemmed Internal Conversion and Vibrational Energy Redistribution in Chlorophyll A
title_sort Internal Conversion and Vibrational Energy Redistribution in Chlorophyll A
dc.creator.none.fl_str_mv Shenai, Prathamesh M.
Fernández Alberti, Sebastián
Bricker, William P.
Tretiak, Sergei
Zhao, Yang
author Shenai, Prathamesh M.
author_facet Shenai, Prathamesh M.
Fernández Alberti, Sebastián
Bricker, William P.
Tretiak, Sergei
Zhao, Yang
author_role author
author2 Fernández Alberti, Sebastián
Bricker, William P.
Tretiak, Sergei
Zhao, Yang
author2_role author
author
author
author
dc.subject.none.fl_str_mv Vibrational Relaxation
Excited States
Normal Modes
Chlorophylls
topic Vibrational Relaxation
Excited States
Normal Modes
Chlorophylls
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We have computationally investigated the role of intramolecular vibrational modes in determining nonradiative relaxation pathways of photoexcited electronic states in isolated chlorophyll A (ChlA) molecules. To simulate the excited state relaxation from the initially excited Soret state to the lowest excited state Qy, the approach of nonadiabatic excited state molecular dynamics has been adopted. The intramolecular vibrational energy relaxation and redistribution that accompany the electronic internal conversion process is followed by analyzing the excited state trajectories in terms of the ground state equilibrium normal modes. The time dependence of the normal mode velocities is determined by projecting instantaneous Cartesian velocities onto the normal mode vectors. Our analysis of the time evolution of the average mode energies uncovers that only a small subset of the medium-to-high frequency normal modes actively participate in the electronic relaxation processes. These active modes are characterized by the highest overlap with the nonadiabatic coupling vectors(NACRs) during the electronic transitions. Further statistical analysis of the nonadiabatic transitions reveals that the electronic and vibrational energy relaxation occurs via two distinct pathways with significantly different time scales on which the hopping from Soret to Qx occurs thereby dictating the overall dynamics. Furthermore, the NACRs corresponding to each of the transitions have been consistently found to be predominantly similar to a set of normal modes that vary depending upon the transition and the identified categories. Each pathway exhibits a differential time scale of energy transfer and also a differential set of predominant active modes. Our present analysis can be considered as a general approach allowing identification of a reducedsubset of specific vibrational coordinates associated with nonradiative relaxation pathways. Therefore, it represents an adequate prior strategy that can particularly facilitates mixed quantum-classical approaches.
Fil: Shenai, Prathamesh M.. Nanyang Technological University; Singapur
Fil: Fernández Alberti, Sebastián. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes; Argentina
Fil: Bricker, William P.. University of Washington; Estados Unidos
Fil: Tretiak, Sergei. Los Alamos National High Magnetic Field Laboratory; Estados Unidos
Fil: Zhao, Yang. Nanyang Technological University; Singapur
description We have computationally investigated the role of intramolecular vibrational modes in determining nonradiative relaxation pathways of photoexcited electronic states in isolated chlorophyll A (ChlA) molecules. To simulate the excited state relaxation from the initially excited Soret state to the lowest excited state Qy, the approach of nonadiabatic excited state molecular dynamics has been adopted. The intramolecular vibrational energy relaxation and redistribution that accompany the electronic internal conversion process is followed by analyzing the excited state trajectories in terms of the ground state equilibrium normal modes. The time dependence of the normal mode velocities is determined by projecting instantaneous Cartesian velocities onto the normal mode vectors. Our analysis of the time evolution of the average mode energies uncovers that only a small subset of the medium-to-high frequency normal modes actively participate in the electronic relaxation processes. These active modes are characterized by the highest overlap with the nonadiabatic coupling vectors(NACRs) during the electronic transitions. Further statistical analysis of the nonadiabatic transitions reveals that the electronic and vibrational energy relaxation occurs via two distinct pathways with significantly different time scales on which the hopping from Soret to Qx occurs thereby dictating the overall dynamics. Furthermore, the NACRs corresponding to each of the transitions have been consistently found to be predominantly similar to a set of normal modes that vary depending upon the transition and the identified categories. Each pathway exhibits a differential time scale of energy transfer and also a differential set of predominant active modes. Our present analysis can be considered as a general approach allowing identification of a reducedsubset of specific vibrational coordinates associated with nonradiative relaxation pathways. Therefore, it represents an adequate prior strategy that can particularly facilitates mixed quantum-classical approaches.
publishDate 2015
dc.date.none.fl_str_mv 2015-12
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/11336/42354
Shenai, Prathamesh M.; Fernández Alberti, Sebastián; Bricker, William P.; Tretiak, Sergei; Zhao, Yang; Internal Conversion and Vibrational Energy Redistribution in Chlorophyll A; American Chemical Society; Journal of Physical Chemistry B; 120; 1; 12-2015; 49-58
1520-6106
CONICET Digital
CONICET
url http://hdl.handle.net/11336/42354
identifier_str_mv Shenai, Prathamesh M.; Fernández Alberti, Sebastián; Bricker, William P.; Tretiak, Sergei; Zhao, Yang; Internal Conversion and Vibrational Energy Redistribution in Chlorophyll A; American Chemical Society; Journal of Physical Chemistry B; 120; 1; 12-2015; 49-58
1520-6106
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/acs.jpcb.5b09548
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcb.5b09548
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
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