Triplet Mediated C−N Dissociation versus Internal Conversion in Electronically Excited N‑Methylpyrrole

The photochemical and photophysical pathways operative in N-methylpyrrole, after excitation in the near part of its ultraviolet absorption spectrum, have been investigated by the combination of time-resolved total ion yield and photoelectron spectroscopies with high-level ab initio calculations. The...

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Detalles Bibliográficos
Autores: Blancafort San José, Lluís, Ovejas, Virginia, Montero, Raúl, Fernández Fernández, Marta, Longarte, Asier
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2016
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/13495
Acceso en línea:http://hdl.handle.net/10256/13495
Access Level:acceso embargado
Palabra clave:Fotoquímica
Photochemistry
Ionització
Ionization
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spelling Triplet Mediated C−N Dissociation versus Internal Conversion in Electronically Excited N‑MethylpyrroleBlancafort San José, LluísOvejas, VirginiaMontero, RaúlFernández Fernández, MartaLongarte, AsierFotoquímicaPhotochemistryIonitzacióIonizationThe photochemical and photophysical pathways operative in N-methylpyrrole, after excitation in the near part of its ultraviolet absorption spectrum, have been investigated by the combination of time-resolved total ion yield and photoelectron spectroscopies with high-level ab initio calculations. The results collected are remarkably different from the observations made for pyrrole and other aromatic systems, whose dynamics is dictated by the presence of πσ* excitations on X–H (X: N, O, S, ...) bonds. The presence of a barrier along the C–N dissociation coordinate that can not be tunneled triggers two alternative decay mechanisms for the S1 A″ πσ* state. While at low vibrational content the C–N dissociation occurs on the surface of a lower 3ππ* state reached after efficient intersystem crossing, at higher excitation energies, the A″ πσ* directly internally converts to the ground state through a ring-twisted S1/S0 conical intersection. The findings explain previous observations on the molecule and may be relevant for more complex systems containing similar C–N bonds, such as the DNA nucleotidesThis work was funded by the “Ayudas para apoyar las actividades de grupos de investigación del sistema universitario vasco” program from the Basque Government, Grant 2014SGR1202 from the Agència de Gestiód’Ajuts Universitaris i de Recerca (AGAUR) from Catalonia (Spain), CTQ2016-69363-P from the Spanish Ministerio de Economıá y Competitividad (MINECO) and UNGI10-4E-801 from the Ministerio de Ciencia e Innovación (MICINN) and the European Fund for Regional Development, and the Xarxa de Refereǹ cia en Quiḿ ica Teor̀ ica i Computacional de Catalunya (AGAUR)American Chemical Society (ACS)Ministerio de Economía y Competitividad (Espanya)infoinfo2016info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10256/13495http://hdl.handle.net/10256/13495© Journal of Physical Chemistry Letters, 2016, vol. 7, núm. 7, p. 1231-1237Articles publicats (D-Q)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpclett.6b00195info:eu-repo/semantics/altIdentifier/issn/1948-7185info:eu-repo/grantAgreement/MINECO//CTQ2015-69363-PTots els drets reservatsinfo:eu-repo/semantics/embargoedAccessoai:recercat.cat:10256/134952026-05-29T05:05:01Z
dc.title.none.fl_str_mv Triplet Mediated C−N Dissociation versus Internal Conversion in Electronically Excited N‑Methylpyrrole
title Triplet Mediated C−N Dissociation versus Internal Conversion in Electronically Excited N‑Methylpyrrole
spellingShingle Triplet Mediated C−N Dissociation versus Internal Conversion in Electronically Excited N‑Methylpyrrole
Blancafort San José, Lluís
Fotoquímica
Photochemistry
Ionització
Ionization
title_short Triplet Mediated C−N Dissociation versus Internal Conversion in Electronically Excited N‑Methylpyrrole
title_full Triplet Mediated C−N Dissociation versus Internal Conversion in Electronically Excited N‑Methylpyrrole
title_fullStr Triplet Mediated C−N Dissociation versus Internal Conversion in Electronically Excited N‑Methylpyrrole
title_full_unstemmed Triplet Mediated C−N Dissociation versus Internal Conversion in Electronically Excited N‑Methylpyrrole
title_sort Triplet Mediated C−N Dissociation versus Internal Conversion in Electronically Excited N‑Methylpyrrole
dc.creator.none.fl_str_mv Blancafort San José, Lluís
Ovejas, Virginia
Montero, Raúl
Fernández Fernández, Marta
Longarte, Asier
author Blancafort San José, Lluís
author_facet Blancafort San José, Lluís
Ovejas, Virginia
Montero, Raúl
Fernández Fernández, Marta
Longarte, Asier
author_role author
author2 Ovejas, Virginia
Montero, Raúl
Fernández Fernández, Marta
Longarte, Asier
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (Espanya)
dc.subject.none.fl_str_mv Fotoquímica
Photochemistry
Ionització
Ionization
topic Fotoquímica
Photochemistry
Ionització
Ionization
description The photochemical and photophysical pathways operative in N-methylpyrrole, after excitation in the near part of its ultraviolet absorption spectrum, have been investigated by the combination of time-resolved total ion yield and photoelectron spectroscopies with high-level ab initio calculations. The results collected are remarkably different from the observations made for pyrrole and other aromatic systems, whose dynamics is dictated by the presence of πσ* excitations on X–H (X: N, O, S, ...) bonds. The presence of a barrier along the C–N dissociation coordinate that can not be tunneled triggers two alternative decay mechanisms for the S1 A″ πσ* state. While at low vibrational content the C–N dissociation occurs on the surface of a lower 3ππ* state reached after efficient intersystem crossing, at higher excitation energies, the A″ πσ* directly internally converts to the ground state through a ring-twisted S1/S0 conical intersection. The findings explain previous observations on the molecule and may be relevant for more complex systems containing similar C–N bonds, such as the DNA nucleotides
publishDate 2016
dc.date.none.fl_str_mv 2016
info
info
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/13495
http://hdl.handle.net/10256/13495
url http://hdl.handle.net/10256/13495
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpclett.6b00195
info:eu-repo/semantics/altIdentifier/issn/1948-7185
info:eu-repo/grantAgreement/MINECO//CTQ2015-69363-P
dc.rights.none.fl_str_mv Tots els drets reservats
info:eu-repo/semantics/embargoedAccess
rights_invalid_str_mv Tots els drets reservats
eu_rights_str_mv embargoedAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society (ACS)
publisher.none.fl_str_mv American Chemical Society (ACS)
dc.source.none.fl_str_mv © Journal of Physical Chemistry Letters, 2016, vol. 7, núm. 7, p. 1231-1237
Articles publicats (D-Q)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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