Monitoring vibronic coherences and molecular aromaticity in photoexcited cyclooctatetraene with an X-ray probe: a simulation study

Autores
Nam, Yeonsig; Song, Huajing; Freixas Lemus, Victor Manuel; Keefer, Daniel; Fernández Alberti, Sebastián; Lee, Jin Yong; Garavelli, Marco; Tretiak, Sergei; Mukamel, Shaul
Año de publicación
2024
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Understanding conical intersection (CI) dynamics and subsequent conformational changes is key for exploring and controlling photo-reactions in aromatic molecules. Monitoring of their time-resolved dynamics remains a formidable experimental challenge. In this study, we simulate the photoinduced S3 to S1 non-adiabatic dynamics of cyclooctatetraene (COT), involving multiple CIs with relaxation times in good agreement with experiment. We further investigate the possibility to directly probe the CI passages in COT by off-resonant X-ray Raman spectroscopy (TRUECARS) and time-resolved X-ray diffraction (TRXD). We find that these signals sensitively monitor key chemical features during the ultrafast dynamics. First, we distinguish two CIs by using TRUECARS signals with their appearances at different Raman shifts. Second, we demonstrate that TRXD, where X-ray photons scatter off electron densities, can resolve ultrafast changes in the aromaticity of COT. It can further distinguish between planar and non-planar geometries explored during the dynamics, as e.g. two different tetraradical-type CIs. The knowledge gained from these measurements can give unique insight into fundamental chemical properties that dynamically change during non-adiabatic passages.
Fil: Nam, Yeonsig. University of California at Irvine; Estados Unidos
Fil: Song, Huajing. Los Alamos National High Magnetic Field Laboratory; Estados Unidos
Fil: Freixas Lemus, Victor Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina
Fil: Keefer, Daniel. University of California at Irvine; Estados Unidos
Fil: Fernández Alberti, Sebastián. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina
Fil: Lee, Jin Yong. University of California at Irvine; Estados Unidos
Fil: Garavelli, Marco. Università di Bologna; Italia
Fil: Tretiak, Sergei. Los Alamos National High Magnetic Field Laboratory; Estados Unidos
Fil: Mukamel, Shaul. University of California at Irvine; Estados Unidos
Materia
Aromacity
ELectronic Coherence
Molecular dynamics
Nivel de accesibilidad
acceso embargado
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:11336/237717
Acceder
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network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Monitoring vibronic coherences and molecular aromaticity in photoexcited cyclooctatetraene with an X-ray probe: a simulation studyNam, YeonsigSong, HuajingFreixas Lemus, Victor ManuelKeefer, DanielFernández Alberti, SebastiánLee, Jin YongGaravelli, MarcoTretiak, SergeiMukamel, ShaulAromacityELectronic CoherenceMolecular dynamicshttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1Understanding conical intersection (CI) dynamics and subsequent conformational changes is key for exploring and controlling photo-reactions in aromatic molecules. Monitoring of their time-resolved dynamics remains a formidable experimental challenge. In this study, we simulate the photoinduced S3 to S1 non-adiabatic dynamics of cyclooctatetraene (COT), involving multiple CIs with relaxation times in good agreement with experiment. We further investigate the possibility to directly probe the CI passages in COT by off-resonant X-ray Raman spectroscopy (TRUECARS) and time-resolved X-ray diffraction (TRXD). We find that these signals sensitively monitor key chemical features during the ultrafast dynamics. First, we distinguish two CIs by using TRUECARS signals with their appearances at different Raman shifts. Second, we demonstrate that TRXD, where X-ray photons scatter off electron densities, can resolve ultrafast changes in the aromaticity of COT. It can further distinguish between planar and non-planar geometries explored during the dynamics, as e.g. two different tetraradical-type CIs. The knowledge gained from these measurements can give unique insight into fundamental chemical properties that dynamically change during non-adiabatic passages.Fil: Nam, Yeonsig. University of California at Irvine; Estados UnidosFil: Song, Huajing. Los Alamos National High Magnetic Field Laboratory; Estados UnidosFil: Freixas Lemus, Victor Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; ArgentinaFil: Keefer, Daniel. University of California at Irvine; Estados UnidosFil: Fernández Alberti, Sebastián. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; ArgentinaFil: Lee, Jin Yong. University of California at Irvine; Estados UnidosFil: Garavelli, Marco. Università di Bologna; ItaliaFil: Tretiak, Sergei. Los Alamos National High Magnetic Field Laboratory; Estados UnidosFil: Mukamel, Shaul. University of California at Irvine; Estados UnidosRoyal Society of Chemistry2024-02info:eu-repo/date/embargoEnd/2024-08-11info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/237717Nam, Yeonsig; Song, Huajing; Freixas Lemus, Victor Manuel; Keefer, Daniel; Fernández Alberti, Sebastián; et al.; Monitoring vibronic coherences and molecular aromaticity in photoexcited cyclooctatetraene with an X-ray probe: a simulation study; Royal Society of Chemistry; Chemical Science; 14; 11; 2-2024; 2971-29822041-6539CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/d2sc04335ainfo:eu-repo/semantics/embargoedAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-11-12T09:40:47Zoai:ri.conicet.gov.ar:11336/237717instacron: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:34982025-11-12 09:40:48.072CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Monitoring vibronic coherences and molecular aromaticity in photoexcited cyclooctatetraene with an X-ray probe: a simulation study
title Monitoring vibronic coherences and molecular aromaticity in photoexcited cyclooctatetraene with an X-ray probe: a simulation study
spellingShingle Monitoring vibronic coherences and molecular aromaticity in photoexcited cyclooctatetraene with an X-ray probe: a simulation study
Nam, Yeonsig
Aromacity
ELectronic Coherence
Molecular dynamics
title_short Monitoring vibronic coherences and molecular aromaticity in photoexcited cyclooctatetraene with an X-ray probe: a simulation study
title_full Monitoring vibronic coherences and molecular aromaticity in photoexcited cyclooctatetraene with an X-ray probe: a simulation study
title_fullStr Monitoring vibronic coherences and molecular aromaticity in photoexcited cyclooctatetraene with an X-ray probe: a simulation study
title_full_unstemmed Monitoring vibronic coherences and molecular aromaticity in photoexcited cyclooctatetraene with an X-ray probe: a simulation study
title_sort Monitoring vibronic coherences and molecular aromaticity in photoexcited cyclooctatetraene with an X-ray probe: a simulation study
dc.creator.none.fl_str_mv Nam, Yeonsig
Song, Huajing
Freixas Lemus, Victor Manuel
Keefer, Daniel
Fernández Alberti, Sebastián
Lee, Jin Yong
Garavelli, Marco
Tretiak, Sergei
Mukamel, Shaul
author Nam, Yeonsig
author_facet Nam, Yeonsig
Song, Huajing
Freixas Lemus, Victor Manuel
Keefer, Daniel
Fernández Alberti, Sebastián
Lee, Jin Yong
Garavelli, Marco
Tretiak, Sergei
Mukamel, Shaul
author_role author
author2 Song, Huajing
Freixas Lemus, Victor Manuel
Keefer, Daniel
Fernández Alberti, Sebastián
Lee, Jin Yong
Garavelli, Marco
Tretiak, Sergei
Mukamel, Shaul
author2_role author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Aromacity
ELectronic Coherence
Molecular dynamics
topic Aromacity
ELectronic Coherence
Molecular dynamics
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Understanding conical intersection (CI) dynamics and subsequent conformational changes is key for exploring and controlling photo-reactions in aromatic molecules. Monitoring of their time-resolved dynamics remains a formidable experimental challenge. In this study, we simulate the photoinduced S3 to S1 non-adiabatic dynamics of cyclooctatetraene (COT), involving multiple CIs with relaxation times in good agreement with experiment. We further investigate the possibility to directly probe the CI passages in COT by off-resonant X-ray Raman spectroscopy (TRUECARS) and time-resolved X-ray diffraction (TRXD). We find that these signals sensitively monitor key chemical features during the ultrafast dynamics. First, we distinguish two CIs by using TRUECARS signals with their appearances at different Raman shifts. Second, we demonstrate that TRXD, where X-ray photons scatter off electron densities, can resolve ultrafast changes in the aromaticity of COT. It can further distinguish between planar and non-planar geometries explored during the dynamics, as e.g. two different tetraradical-type CIs. The knowledge gained from these measurements can give unique insight into fundamental chemical properties that dynamically change during non-adiabatic passages.
Fil: Nam, Yeonsig. University of California at Irvine; Estados Unidos
Fil: Song, Huajing. Los Alamos National High Magnetic Field Laboratory; Estados Unidos
Fil: Freixas Lemus, Victor Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina
Fil: Keefer, Daniel. University of California at Irvine; Estados Unidos
Fil: Fernández Alberti, Sebastián. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina
Fil: Lee, Jin Yong. University of California at Irvine; Estados Unidos
Fil: Garavelli, Marco. Università di Bologna; Italia
Fil: Tretiak, Sergei. Los Alamos National High Magnetic Field Laboratory; Estados Unidos
Fil: Mukamel, Shaul. University of California at Irvine; Estados Unidos
description Understanding conical intersection (CI) dynamics and subsequent conformational changes is key for exploring and controlling photo-reactions in aromatic molecules. Monitoring of their time-resolved dynamics remains a formidable experimental challenge. In this study, we simulate the photoinduced S3 to S1 non-adiabatic dynamics of cyclooctatetraene (COT), involving multiple CIs with relaxation times in good agreement with experiment. We further investigate the possibility to directly probe the CI passages in COT by off-resonant X-ray Raman spectroscopy (TRUECARS) and time-resolved X-ray diffraction (TRXD). We find that these signals sensitively monitor key chemical features during the ultrafast dynamics. First, we distinguish two CIs by using TRUECARS signals with their appearances at different Raman shifts. Second, we demonstrate that TRXD, where X-ray photons scatter off electron densities, can resolve ultrafast changes in the aromaticity of COT. It can further distinguish between planar and non-planar geometries explored during the dynamics, as e.g. two different tetraradical-type CIs. The knowledge gained from these measurements can give unique insight into fundamental chemical properties that dynamically change during non-adiabatic passages.
publishDate 2024
dc.date.none.fl_str_mv 2024-02
info:eu-repo/date/embargoEnd/2024-08-11
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/11336/237717
Nam, Yeonsig; Song, Huajing; Freixas Lemus, Victor Manuel; Keefer, Daniel; Fernández Alberti, Sebastián; et al.; Monitoring vibronic coherences and molecular aromaticity in photoexcited cyclooctatetraene with an X-ray probe: a simulation study; Royal Society of Chemistry; Chemical Science; 14; 11; 2-2024; 2971-2982
2041-6539
CONICET Digital
CONICET
url http://hdl.handle.net/11336/237717
identifier_str_mv Nam, Yeonsig; Song, Huajing; Freixas Lemus, Victor Manuel; Keefer, Daniel; Fernández Alberti, Sebastián; et al.; Monitoring vibronic coherences and molecular aromaticity in photoexcited cyclooctatetraene with an X-ray probe: a simulation study; Royal Society of Chemistry; Chemical Science; 14; 11; 2-2024; 2971-2982
2041-6539
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/d2sc04335a
dc.rights.none.fl_str_mv info:eu-repo/semantics/embargoedAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv embargoedAccess
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 Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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 13.24909

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