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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/42354
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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 |
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CONICET Digital (CONICET) |
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CONICET Digital (CONICET) |
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Consejo Nacional de Investigaciones Científicas y Técnicas |
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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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1844614500930551808 |
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13.070432 |