Excited state hydrogen transfer dynamics in substituted phenols and their complexes with ammonia: π π * -π σ*energy gap propensity and ortho-substitution effect

Autores
Pino, Gustavo Ariel; Oldani, Andres Nicolas; Marceca, Ernesto José; Fujii, M.; Ishiuchi, S.-I.; Miyazaki, M.; Broquier, M.; Dedonder, C.; Jouvet, C.
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Lifetimes of the first electronic excited state (S1) of fluorine and methyl (o-, m-, and p-) substituted phenols and their complexes with one ammonia molecule have been measured for the 00 transition and for the intermolecular stretching σ1 levels in complexes using picosecond pump-probe spectroscopy. Excitation energies to the S1 (π π *) and S2 (π σ*) states are obtained by quantum chemical calculations at the MP2 and CC2 level using the aug-cc-pVDZ basis set for the ground-state and the S1 optimized geometries. The observed lifetimes and the energy gaps between the π π * and π σ* states show a good correlation, the lifetime being shorter for a smaller energy gap. This propensity suggests that the major dynamics in the excited state concerns an excited state hydrogen detachment or transfer (ESHD/T) promoted directly by a S1 / S2 conical intersection, rather than via internal conversion to the ground-state. A specific shortening of lifetime is found in the o-fluorophenol-ammonia complex and explained in terms of the vibronic coupling between the π π * and π σ* states occurring through the out-of-plane distortion of the C-F bond.
Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Oldani, Andres Nicolas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Marceca, Ernesto José. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Fujii, M.. Tokyo Institute of Technology; Japón
Fil: Ishiuchi, S.-I.. Tokyo Institute of Technology; Japón
Fil: Miyazaki, M.. Tokyo Institute of Technology; Japón
Fil: Broquier, M.. Centre National de la Recherche Scientifique; Francia. Universite Paris-Saclay;
Fil: Dedonder, C.. Centre National de la Recherche Scientifique; Francia. Universite Paris-Saclay;
Fil: Jouvet, C.. Universite Paris-Saclay; . Centre National de la Recherche Scientifique; Francia
Materia
ESHT/D
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:11336/190793
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/190793
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Excited state hydrogen transfer dynamics in substituted phenols and their complexes with ammonia: π π * -π σ*energy gap propensity and ortho-substitution effectPino, Gustavo ArielOldani, Andres NicolasMarceca, Ernesto JoséFujii, M.Ishiuchi, S.-I.Miyazaki, M.Broquier, M.Dedonder, C.Jouvet, C.ESHT/Dhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Lifetimes of the first electronic excited state (S1) of fluorine and methyl (o-, m-, and p-) substituted phenols and their complexes with one ammonia molecule have been measured for the 00 transition and for the intermolecular stretching σ1 levels in complexes using picosecond pump-probe spectroscopy. Excitation energies to the S1 (π π *) and S2 (π σ*) states are obtained by quantum chemical calculations at the MP2 and CC2 level using the aug-cc-pVDZ basis set for the ground-state and the S1 optimized geometries. The observed lifetimes and the energy gaps between the π π * and π σ* states show a good correlation, the lifetime being shorter for a smaller energy gap. This propensity suggests that the major dynamics in the excited state concerns an excited state hydrogen detachment or transfer (ESHD/T) promoted directly by a S1 / S2 conical intersection, rather than via internal conversion to the ground-state. A specific shortening of lifetime is found in the o-fluorophenol-ammonia complex and explained in terms of the vibronic coupling between the π π * and π σ* states occurring through the out-of-plane distortion of the C-F bond.Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Oldani, Andres Nicolas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Marceca, Ernesto José. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Fujii, M.. Tokyo Institute of Technology; JapónFil: Ishiuchi, S.-I.. Tokyo Institute of Technology; JapónFil: Miyazaki, M.. Tokyo Institute of Technology; JapónFil: Broquier, M.. Centre National de la Recherche Scientifique; Francia. Universite Paris-Saclay;Fil: Dedonder, C.. Centre National de la Recherche Scientifique; Francia. Universite Paris-Saclay;Fil: Jouvet, C.. Universite Paris-Saclay; . Centre National de la Recherche Scientifique; FranciaAmerican Institute of Physics2010-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/190793Pino, Gustavo Ariel; Oldani, Andres Nicolas; Marceca, Ernesto José; Fujii, M.; Ishiuchi, S.-I.; et al.; Excited state hydrogen transfer dynamics in substituted phenols and their complexes with ammonia: π π * -π σ*energy gap propensity and ortho-substitution effect; American Institute of Physics; Journal of Chemical Physics; 133; 12; 9-2010; 1-120021-9606CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://aip.scitation.org/doi/10.1063/1.3480396info:eu-repo/semantics/altIdentifier/doi/10.1063/1.3480396info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:19:49Zoai:ri.conicet.gov.ar:11336/190793instacron: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 10:19:49.315CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Excited state hydrogen transfer dynamics in substituted phenols and their complexes with ammonia: π π * -π σ*energy gap propensity and ortho-substitution effect
title Excited state hydrogen transfer dynamics in substituted phenols and their complexes with ammonia: π π * -π σ*energy gap propensity and ortho-substitution effect
spellingShingle Excited state hydrogen transfer dynamics in substituted phenols and their complexes with ammonia: π π * -π σ*energy gap propensity and ortho-substitution effect
Pino, Gustavo Ariel
ESHT/D
title_short Excited state hydrogen transfer dynamics in substituted phenols and their complexes with ammonia: π π * -π σ*energy gap propensity and ortho-substitution effect
title_full Excited state hydrogen transfer dynamics in substituted phenols and their complexes with ammonia: π π * -π σ*energy gap propensity and ortho-substitution effect
title_fullStr Excited state hydrogen transfer dynamics in substituted phenols and their complexes with ammonia: π π * -π σ*energy gap propensity and ortho-substitution effect
title_full_unstemmed Excited state hydrogen transfer dynamics in substituted phenols and their complexes with ammonia: π π * -π σ*energy gap propensity and ortho-substitution effect
title_sort Excited state hydrogen transfer dynamics in substituted phenols and their complexes with ammonia: π π * -π σ*energy gap propensity and ortho-substitution effect
dc.creator.none.fl_str_mv Pino, Gustavo Ariel
Oldani, Andres Nicolas
Marceca, Ernesto José
Fujii, M.
Ishiuchi, S.-I.
Miyazaki, M.
Broquier, M.
Dedonder, C.
Jouvet, C.
author Pino, Gustavo Ariel
author_facet Pino, Gustavo Ariel
Oldani, Andres Nicolas
Marceca, Ernesto José
Fujii, M.
Ishiuchi, S.-I.
Miyazaki, M.
Broquier, M.
Dedonder, C.
Jouvet, C.
author_role author
author2 Oldani, Andres Nicolas
Marceca, Ernesto José
Fujii, M.
Ishiuchi, S.-I.
Miyazaki, M.
Broquier, M.
Dedonder, C.
Jouvet, C.
author2_role author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv ESHT/D
topic ESHT/D
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Lifetimes of the first electronic excited state (S1) of fluorine and methyl (o-, m-, and p-) substituted phenols and their complexes with one ammonia molecule have been measured for the 00 transition and for the intermolecular stretching σ1 levels in complexes using picosecond pump-probe spectroscopy. Excitation energies to the S1 (π π *) and S2 (π σ*) states are obtained by quantum chemical calculations at the MP2 and CC2 level using the aug-cc-pVDZ basis set for the ground-state and the S1 optimized geometries. The observed lifetimes and the energy gaps between the π π * and π σ* states show a good correlation, the lifetime being shorter for a smaller energy gap. This propensity suggests that the major dynamics in the excited state concerns an excited state hydrogen detachment or transfer (ESHD/T) promoted directly by a S1 / S2 conical intersection, rather than via internal conversion to the ground-state. A specific shortening of lifetime is found in the o-fluorophenol-ammonia complex and explained in terms of the vibronic coupling between the π π * and π σ* states occurring through the out-of-plane distortion of the C-F bond.
Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Oldani, Andres Nicolas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Marceca, Ernesto José. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Fujii, M.. Tokyo Institute of Technology; Japón
Fil: Ishiuchi, S.-I.. Tokyo Institute of Technology; Japón
Fil: Miyazaki, M.. Tokyo Institute of Technology; Japón
Fil: Broquier, M.. Centre National de la Recherche Scientifique; Francia. Universite Paris-Saclay;
Fil: Dedonder, C.. Centre National de la Recherche Scientifique; Francia. Universite Paris-Saclay;
Fil: Jouvet, C.. Universite Paris-Saclay; . Centre National de la Recherche Scientifique; Francia
description Lifetimes of the first electronic excited state (S1) of fluorine and methyl (o-, m-, and p-) substituted phenols and their complexes with one ammonia molecule have been measured for the 00 transition and for the intermolecular stretching σ1 levels in complexes using picosecond pump-probe spectroscopy. Excitation energies to the S1 (π π *) and S2 (π σ*) states are obtained by quantum chemical calculations at the MP2 and CC2 level using the aug-cc-pVDZ basis set for the ground-state and the S1 optimized geometries. The observed lifetimes and the energy gaps between the π π * and π σ* states show a good correlation, the lifetime being shorter for a smaller energy gap. This propensity suggests that the major dynamics in the excited state concerns an excited state hydrogen detachment or transfer (ESHD/T) promoted directly by a S1 / S2 conical intersection, rather than via internal conversion to the ground-state. A specific shortening of lifetime is found in the o-fluorophenol-ammonia complex and explained in terms of the vibronic coupling between the π π * and π σ* states occurring through the out-of-plane distortion of the C-F bond.
publishDate 2010
dc.date.none.fl_str_mv 2010-09
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/11336/190793
Pino, Gustavo Ariel; Oldani, Andres Nicolas; Marceca, Ernesto José; Fujii, M.; Ishiuchi, S.-I.; et al.; Excited state hydrogen transfer dynamics in substituted phenols and their complexes with ammonia: π π * -π σ*energy gap propensity and ortho-substitution effect; American Institute of Physics; Journal of Chemical Physics; 133; 12; 9-2010; 1-12
0021-9606
CONICET Digital
CONICET
url http://hdl.handle.net/11336/190793
identifier_str_mv Pino, Gustavo Ariel; Oldani, Andres Nicolas; Marceca, Ernesto José; Fujii, M.; Ishiuchi, S.-I.; et al.; Excited state hydrogen transfer dynamics in substituted phenols and their complexes with ammonia: π π * -π σ*energy gap propensity and ortho-substitution effect; American Institute of Physics; Journal of Chemical Physics; 133; 12; 9-2010; 1-12
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/https://aip.scitation.org/doi/10.1063/1.3480396
info:eu-repo/semantics/altIdentifier/doi/10.1063/1.3480396
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 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 13.070432

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