Ultrafast ring-opening and solvent-dependent product relaxation of photochromic spironaphthopyran

Autores
Bittmann, Simon F.; Dsouza, Raison; Siddiqui, Khalid M.; Hayes, Stuart A.; Rossos, Andreas; Corthey, Gastón; Kochman, Michal; Prokhorenko, Valentyn I.; Murphy, R. Scott; Schwoerer, Heinrich; Miller, R. J. Dwayne
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The ultrafast dynamics of unsubstituted spironaphthopyran (SNP) were investigated using femtosecond transient UV and visible absorption spectroscopy in three different solvents and by semi-classical nuclear dynamics simulations. The primary ring-opening of the pyran unit was found to occur in 300 fs yielding a non-planar intermediate in the first singlet excited state (S1). Subsequent planarisation and relaxation to the product ground state proceed through barrier crossing on the S1 potential energy surface (PES) and take place within 1.1 ps after excitation. Simulations show that more than 90% of the trajectories involving C–O bond elongation lead to the planar, open-ring product, while relaxation back to the S0 of the closed-ring form is accompanied by C–N elongation. All ensuing spectral dynamics are ascribed to vibrational relaxation and thermalisation of the product with a time constant of 13 ps. The latter shows dependency on characteristics of the solvent with solvent relaxation kinetics playing a role.
Fil: Bittmann, Simon F.. Max Planck Institute for the Structure and Dynamics of Matter; Alemania
Fil: Dsouza, Raison. Max Planck Institute for the Structure and Dynamics of Matter; Alemania. Universitat Hamburg; Alemania
Fil: Siddiqui, Khalid M.. Max Planck Institute for the Structure and Dynamics of Matter; Alemania
Fil: Hayes, Stuart A.. Max Planck Institute for the Structure and Dynamics of Matter; Alemania
Fil: Rossos, Andreas. Max Planck Institute for the Structure and Dynamics of Matter; Alemania
Fil: Corthey, Gastón. Max Planck Institute for the Structure and Dynamics of Matter; Alemania. Universidad Nacional de San Martin. Instituto de Nanosistemas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Kochman, Michal. Max Planck Institute for the Structure and Dynamics of Matter; Alemania. Linköping University; Suecia
Fil: Prokhorenko, Valentyn I.. Max Planck Institute for the Structure and Dynamics of Matter; Alemania
Fil: Murphy, R. Scott. University of Regina; Canadá
Fil: Schwoerer, Heinrich. Max Planck Institute for the Structure and Dynamics of Matter; Alemania
Fil: Miller, R. J. Dwayne. University of Toronto; Canadá. Max Planck Institute for the Structure and Dynamics of Matter; Alemania
Materia
ULTRAFAST
SPECTROSCOPY
PUMP-PROBE
Spironaphthopyran
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/155447
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/155447
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Ultrafast ring-opening and solvent-dependent product relaxation of photochromic spironaphthopyranBittmann, Simon F.Dsouza, RaisonSiddiqui, Khalid M.Hayes, Stuart A.Rossos, AndreasCorthey, GastónKochman, MichalProkhorenko, Valentyn I.Murphy, R. ScottSchwoerer, HeinrichMiller, R. J. DwayneULTRAFASTSPECTROSCOPYPUMP-PROBESpironaphthopyranhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The ultrafast dynamics of unsubstituted spironaphthopyran (SNP) were investigated using femtosecond transient UV and visible absorption spectroscopy in three different solvents and by semi-classical nuclear dynamics simulations. The primary ring-opening of the pyran unit was found to occur in 300 fs yielding a non-planar intermediate in the first singlet excited state (S1). Subsequent planarisation and relaxation to the product ground state proceed through barrier crossing on the S1 potential energy surface (PES) and take place within 1.1 ps after excitation. Simulations show that more than 90% of the trajectories involving C–O bond elongation lead to the planar, open-ring product, while relaxation back to the S0 of the closed-ring form is accompanied by C–N elongation. All ensuing spectral dynamics are ascribed to vibrational relaxation and thermalisation of the product with a time constant of 13 ps. The latter shows dependency on characteristics of the solvent with solvent relaxation kinetics playing a role.Fil: Bittmann, Simon F.. Max Planck Institute for the Structure and Dynamics of Matter; AlemaniaFil: Dsouza, Raison. Max Planck Institute for the Structure and Dynamics of Matter; Alemania. Universitat Hamburg; AlemaniaFil: Siddiqui, Khalid M.. Max Planck Institute for the Structure and Dynamics of Matter; AlemaniaFil: Hayes, Stuart A.. Max Planck Institute for the Structure and Dynamics of Matter; AlemaniaFil: Rossos, Andreas. Max Planck Institute for the Structure and Dynamics of Matter; AlemaniaFil: Corthey, Gastón. Max Planck Institute for the Structure and Dynamics of Matter; Alemania. Universidad Nacional de San Martin. Instituto de Nanosistemas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Kochman, Michal. Max Planck Institute for the Structure and Dynamics of Matter; Alemania. Linköping University; SueciaFil: Prokhorenko, Valentyn I.. Max Planck Institute for the Structure and Dynamics of Matter; AlemaniaFil: Murphy, R. Scott. University of Regina; CanadáFil: Schwoerer, Heinrich. Max Planck Institute for the Structure and Dynamics of Matter; AlemaniaFil: Miller, R. J. Dwayne. University of Toronto; Canadá. Max Planck Institute for the Structure and Dynamics of Matter; AlemaniaRoyal Society of Chemistry2019-08-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/155447Bittmann, Simon F.; Dsouza, Raison; Siddiqui, Khalid M.; Hayes, Stuart A.; Rossos, Andreas; et al.; Ultrafast ring-opening and solvent-dependent product relaxation of photochromic spironaphthopyran; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 21; 33; 8-8-2019; 18119-181271463-9076CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2019/cp/c9cp02950hinfo:eu-repo/semantics/altIdentifier/doi/10.1039/c9cp02950hinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:05:55Zoai:ri.conicet.gov.ar:11336/155447instacron: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 10:05:55.557CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Ultrafast ring-opening and solvent-dependent product relaxation of photochromic spironaphthopyran
title Ultrafast ring-opening and solvent-dependent product relaxation of photochromic spironaphthopyran
spellingShingle Ultrafast ring-opening and solvent-dependent product relaxation of photochromic spironaphthopyran
Bittmann, Simon F.
ULTRAFAST
SPECTROSCOPY
PUMP-PROBE
Spironaphthopyran
title_short Ultrafast ring-opening and solvent-dependent product relaxation of photochromic spironaphthopyran
title_full Ultrafast ring-opening and solvent-dependent product relaxation of photochromic spironaphthopyran
title_fullStr Ultrafast ring-opening and solvent-dependent product relaxation of photochromic spironaphthopyran
title_full_unstemmed Ultrafast ring-opening and solvent-dependent product relaxation of photochromic spironaphthopyran
title_sort Ultrafast ring-opening and solvent-dependent product relaxation of photochromic spironaphthopyran
dc.creator.none.fl_str_mv Bittmann, Simon F.
Dsouza, Raison
Siddiqui, Khalid M.
Hayes, Stuart A.
Rossos, Andreas
Corthey, Gastón
Kochman, Michal
Prokhorenko, Valentyn I.
Murphy, R. Scott
Schwoerer, Heinrich
Miller, R. J. Dwayne
author Bittmann, Simon F.
author_facet Bittmann, Simon F.
Dsouza, Raison
Siddiqui, Khalid M.
Hayes, Stuart A.
Rossos, Andreas
Corthey, Gastón
Kochman, Michal
Prokhorenko, Valentyn I.
Murphy, R. Scott
Schwoerer, Heinrich
Miller, R. J. Dwayne
author_role author
author2 Dsouza, Raison
Siddiqui, Khalid M.
Hayes, Stuart A.
Rossos, Andreas
Corthey, Gastón
Kochman, Michal
Prokhorenko, Valentyn I.
Murphy, R. Scott
Schwoerer, Heinrich
Miller, R. J. Dwayne
author2_role author
author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv ULTRAFAST
SPECTROSCOPY
PUMP-PROBE
Spironaphthopyran
topic ULTRAFAST
SPECTROSCOPY
PUMP-PROBE
Spironaphthopyran
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 ultrafast dynamics of unsubstituted spironaphthopyran (SNP) were investigated using femtosecond transient UV and visible absorption spectroscopy in three different solvents and by semi-classical nuclear dynamics simulations. The primary ring-opening of the pyran unit was found to occur in 300 fs yielding a non-planar intermediate in the first singlet excited state (S1). Subsequent planarisation and relaxation to the product ground state proceed through barrier crossing on the S1 potential energy surface (PES) and take place within 1.1 ps after excitation. Simulations show that more than 90% of the trajectories involving C–O bond elongation lead to the planar, open-ring product, while relaxation back to the S0 of the closed-ring form is accompanied by C–N elongation. All ensuing spectral dynamics are ascribed to vibrational relaxation and thermalisation of the product with a time constant of 13 ps. The latter shows dependency on characteristics of the solvent with solvent relaxation kinetics playing a role.
Fil: Bittmann, Simon F.. Max Planck Institute for the Structure and Dynamics of Matter; Alemania
Fil: Dsouza, Raison. Max Planck Institute for the Structure and Dynamics of Matter; Alemania. Universitat Hamburg; Alemania
Fil: Siddiqui, Khalid M.. Max Planck Institute for the Structure and Dynamics of Matter; Alemania
Fil: Hayes, Stuart A.. Max Planck Institute for the Structure and Dynamics of Matter; Alemania
Fil: Rossos, Andreas. Max Planck Institute for the Structure and Dynamics of Matter; Alemania
Fil: Corthey, Gastón. Max Planck Institute for the Structure and Dynamics of Matter; Alemania. Universidad Nacional de San Martin. Instituto de Nanosistemas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Kochman, Michal. Max Planck Institute for the Structure and Dynamics of Matter; Alemania. Linköping University; Suecia
Fil: Prokhorenko, Valentyn I.. Max Planck Institute for the Structure and Dynamics of Matter; Alemania
Fil: Murphy, R. Scott. University of Regina; Canadá
Fil: Schwoerer, Heinrich. Max Planck Institute for the Structure and Dynamics of Matter; Alemania
Fil: Miller, R. J. Dwayne. University of Toronto; Canadá. Max Planck Institute for the Structure and Dynamics of Matter; Alemania
description The ultrafast dynamics of unsubstituted spironaphthopyran (SNP) were investigated using femtosecond transient UV and visible absorption spectroscopy in three different solvents and by semi-classical nuclear dynamics simulations. The primary ring-opening of the pyran unit was found to occur in 300 fs yielding a non-planar intermediate in the first singlet excited state (S1). Subsequent planarisation and relaxation to the product ground state proceed through barrier crossing on the S1 potential energy surface (PES) and take place within 1.1 ps after excitation. Simulations show that more than 90% of the trajectories involving C–O bond elongation lead to the planar, open-ring product, while relaxation back to the S0 of the closed-ring form is accompanied by C–N elongation. All ensuing spectral dynamics are ascribed to vibrational relaxation and thermalisation of the product with a time constant of 13 ps. The latter shows dependency on characteristics of the solvent with solvent relaxation kinetics playing a role.
publishDate 2019
dc.date.none.fl_str_mv 2019-08-08
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/11336/155447
Bittmann, Simon F.; Dsouza, Raison; Siddiqui, Khalid M.; Hayes, Stuart A.; Rossos, Andreas; et al.; Ultrafast ring-opening and solvent-dependent product relaxation of photochromic spironaphthopyran; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 21; 33; 8-8-2019; 18119-18127
1463-9076
CONICET Digital
CONICET
url http://hdl.handle.net/11336/155447
identifier_str_mv Bittmann, Simon F.; Dsouza, Raison; Siddiqui, Khalid M.; Hayes, Stuart A.; Rossos, Andreas; et al.; Ultrafast ring-opening and solvent-dependent product relaxation of photochromic spironaphthopyran; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 21; 33; 8-8-2019; 18119-18127
1463-9076
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.rsc.org/en/content/articlelanding/2019/cp/c9cp02950h
info:eu-repo/semantics/altIdentifier/doi/10.1039/c9cp02950h
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/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
_version_ 1842269934384578560
score 13.13397

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