Photofragmentation Mechanisms of Chlorosulfonyl Isocyanate, ClSO2NCO, Excited with Synchrotron Radiation between 12 and 550 eV

Autores
Moreno Betancourt, Angelica; Bava, Yanina Belén; Berrueta Martinez, Yanina; Erben, Mauricio Federico; Cavasso Filho Reinaldo L.; Della Védova, Carlos Omar; Romano, Rosana Mariel
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The unimolecular photofragmentation mechanisms of chlorosulfonyl isocyanate, ClSO2NCO, excited with tunable synchrotron radiation between 12 and 550 eV, were investigated by means of time-of-flight (TOF) coincidence techniques. The main fragmentation mechanism after single ionization, produced by irradiation of an effusive beam of the sample with synchrotron light in the valence electron region, occurs through the breaking of the Cl-S single bond, giving a chloride radical and a SO2NCO+ fragment. This mechanism contrasts with the one observed for the related FSO2NCO, in which the rupture of the S-N bond originates the FSO2+ fragment. The energies of the shallow- (S 2p, Cl 2p, and S 2s) and core-shell (C 1s, N 1s, and O 1s) electrons were determined by X-ray absorption. Transitions between these shallow and core electrons to unoccupied molecular orbitals were also observed in the total ion yield (TIY) spectra. Fourteen different fragmentation mechanisms of the doubly charged parent ion, ClSO2NCO2+, were inferred from the bidimensional photoelectron-photoion-photoion-coincidence (PEPIPICO) spectra. The rupture of the S-N bond can evolve to form NCO+/SO2•+, NCO+/SO•+, or S•+/NCO+ pairs of ions. The Cl-S bond breaking originates different mechanisms, Cl+/SO•+, Cl+/S•+, CO•+/S•+, O•+/SO•+, O•+/Cl+, O•+/S•+, C•+/S•+, and C•+/O•+ pairs being detected in coincidence as the final species. Another three coincidence islands can only be explained with an initial atomic rearrangement forming ClNCO2+, ONCO2+, and ClCO2+, as precursors of CO•+/Cl+, O•+/CO•+, and C•+/Cl+ pairs, respectively. The formation of Cl• radical is deduced from several mechanisms. (Figure Presented).
Fil: Moreno Betancourt, Angelica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Bava, Yanina Belén. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Berrueta Martinez, Yanina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Erben, Mauricio Federico. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Cavasso Filho Reinaldo L.. Universidade Federal do ABC; Brasil
Fil: Della Védova, Carlos Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Romano, Rosana Mariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Materia
Photofragmentation
Synchrotron
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:11336/65858
Acceder
id CONICETDig_b3fe9b4435f2f3eadf913ab611a1bb92
oai_identifier_str oai:ri.conicet.gov.ar:11336/65858
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Photofragmentation Mechanisms of Chlorosulfonyl Isocyanate, ClSO2NCO, Excited with Synchrotron Radiation between 12 and 550 eVMoreno Betancourt, AngelicaBava, Yanina BelénBerrueta Martinez, YaninaErben, Mauricio FedericoCavasso Filho Reinaldo L.Della Védova, Carlos OmarRomano, Rosana MarielPhotofragmentationSynchrotronhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The unimolecular photofragmentation mechanisms of chlorosulfonyl isocyanate, ClSO2NCO, excited with tunable synchrotron radiation between 12 and 550 eV, were investigated by means of time-of-flight (TOF) coincidence techniques. The main fragmentation mechanism after single ionization, produced by irradiation of an effusive beam of the sample with synchrotron light in the valence electron region, occurs through the breaking of the Cl-S single bond, giving a chloride radical and a SO2NCO+ fragment. This mechanism contrasts with the one observed for the related FSO2NCO, in which the rupture of the S-N bond originates the FSO2+ fragment. The energies of the shallow- (S 2p, Cl 2p, and S 2s) and core-shell (C 1s, N 1s, and O 1s) electrons were determined by X-ray absorption. Transitions between these shallow and core electrons to unoccupied molecular orbitals were also observed in the total ion yield (TIY) spectra. Fourteen different fragmentation mechanisms of the doubly charged parent ion, ClSO2NCO2+, were inferred from the bidimensional photoelectron-photoion-photoion-coincidence (PEPIPICO) spectra. The rupture of the S-N bond can evolve to form NCO+/SO2•+, NCO+/SO•+, or S•+/NCO+ pairs of ions. The Cl-S bond breaking originates different mechanisms, Cl+/SO•+, Cl+/S•+, CO•+/S•+, O•+/SO•+, O•+/Cl+, O•+/S•+, C•+/S•+, and C•+/O•+ pairs being detected in coincidence as the final species. Another three coincidence islands can only be explained with an initial atomic rearrangement forming ClNCO2+, ONCO2+, and ClCO2+, as precursors of CO•+/Cl+, O•+/CO•+, and C•+/Cl+ pairs, respectively. The formation of Cl• radical is deduced from several mechanisms. (Figure Presented).Fil: Moreno Betancourt, Angelica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaFil: Bava, Yanina Belén. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaFil: Berrueta Martinez, Yanina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaFil: Erben, Mauricio Federico. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaFil: Cavasso Filho Reinaldo L.. Universidade Federal do ABC; BrasilFil: Della Védova, Carlos Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaFil: Romano, Rosana Mariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaAmerican Chemical Society2015-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/65858Moreno Betancourt, Angelica; Bava, Yanina Belén; Berrueta Martinez, Yanina; Erben, Mauricio Federico; Cavasso Filho Reinaldo L.; et al.; Photofragmentation Mechanisms of Chlorosulfonyl Isocyanate, ClSO2NCO, Excited with Synchrotron Radiation between 12 and 550 eV; American Chemical Society; Journal of Physical Chemistry A; 119; 29; 7-2015; 8021-80301089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/acs.jpca.5b02396info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.5b02396info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:50:19Zoai:ri.conicet.gov.ar:11336/65858instacron: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 09:50:19.667CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Photofragmentation Mechanisms of Chlorosulfonyl Isocyanate, ClSO2NCO, Excited with Synchrotron Radiation between 12 and 550 eV
title Photofragmentation Mechanisms of Chlorosulfonyl Isocyanate, ClSO2NCO, Excited with Synchrotron Radiation between 12 and 550 eV
spellingShingle Photofragmentation Mechanisms of Chlorosulfonyl Isocyanate, ClSO2NCO, Excited with Synchrotron Radiation between 12 and 550 eV
Moreno Betancourt, Angelica
Photofragmentation
Synchrotron
title_short Photofragmentation Mechanisms of Chlorosulfonyl Isocyanate, ClSO2NCO, Excited with Synchrotron Radiation between 12 and 550 eV
title_full Photofragmentation Mechanisms of Chlorosulfonyl Isocyanate, ClSO2NCO, Excited with Synchrotron Radiation between 12 and 550 eV
title_fullStr Photofragmentation Mechanisms of Chlorosulfonyl Isocyanate, ClSO2NCO, Excited with Synchrotron Radiation between 12 and 550 eV
title_full_unstemmed Photofragmentation Mechanisms of Chlorosulfonyl Isocyanate, ClSO2NCO, Excited with Synchrotron Radiation between 12 and 550 eV
title_sort Photofragmentation Mechanisms of Chlorosulfonyl Isocyanate, ClSO2NCO, Excited with Synchrotron Radiation between 12 and 550 eV
dc.creator.none.fl_str_mv Moreno Betancourt, Angelica
Bava, Yanina Belén
Berrueta Martinez, Yanina
Erben, Mauricio Federico
Cavasso Filho Reinaldo L.
Della Védova, Carlos Omar
Romano, Rosana Mariel
author Moreno Betancourt, Angelica
author_facet Moreno Betancourt, Angelica
Bava, Yanina Belén
Berrueta Martinez, Yanina
Erben, Mauricio Federico
Cavasso Filho Reinaldo L.
Della Védova, Carlos Omar
Romano, Rosana Mariel
author_role author
author2 Bava, Yanina Belén
Berrueta Martinez, Yanina
Erben, Mauricio Federico
Cavasso Filho Reinaldo L.
Della Védova, Carlos Omar
Romano, Rosana Mariel
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Photofragmentation
Synchrotron
topic Photofragmentation
Synchrotron
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 unimolecular photofragmentation mechanisms of chlorosulfonyl isocyanate, ClSO2NCO, excited with tunable synchrotron radiation between 12 and 550 eV, were investigated by means of time-of-flight (TOF) coincidence techniques. The main fragmentation mechanism after single ionization, produced by irradiation of an effusive beam of the sample with synchrotron light in the valence electron region, occurs through the breaking of the Cl-S single bond, giving a chloride radical and a SO2NCO+ fragment. This mechanism contrasts with the one observed for the related FSO2NCO, in which the rupture of the S-N bond originates the FSO2+ fragment. The energies of the shallow- (S 2p, Cl 2p, and S 2s) and core-shell (C 1s, N 1s, and O 1s) electrons were determined by X-ray absorption. Transitions between these shallow and core electrons to unoccupied molecular orbitals were also observed in the total ion yield (TIY) spectra. Fourteen different fragmentation mechanisms of the doubly charged parent ion, ClSO2NCO2+, were inferred from the bidimensional photoelectron-photoion-photoion-coincidence (PEPIPICO) spectra. The rupture of the S-N bond can evolve to form NCO+/SO2•+, NCO+/SO•+, or S•+/NCO+ pairs of ions. The Cl-S bond breaking originates different mechanisms, Cl+/SO•+, Cl+/S•+, CO•+/S•+, O•+/SO•+, O•+/Cl+, O•+/S•+, C•+/S•+, and C•+/O•+ pairs being detected in coincidence as the final species. Another three coincidence islands can only be explained with an initial atomic rearrangement forming ClNCO2+, ONCO2+, and ClCO2+, as precursors of CO•+/Cl+, O•+/CO•+, and C•+/Cl+ pairs, respectively. The formation of Cl• radical is deduced from several mechanisms. (Figure Presented).
Fil: Moreno Betancourt, Angelica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Bava, Yanina Belén. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Berrueta Martinez, Yanina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Erben, Mauricio Federico. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Cavasso Filho Reinaldo L.. Universidade Federal do ABC; Brasil
Fil: Della Védova, Carlos Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Romano, Rosana Mariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
description The unimolecular photofragmentation mechanisms of chlorosulfonyl isocyanate, ClSO2NCO, excited with tunable synchrotron radiation between 12 and 550 eV, were investigated by means of time-of-flight (TOF) coincidence techniques. The main fragmentation mechanism after single ionization, produced by irradiation of an effusive beam of the sample with synchrotron light in the valence electron region, occurs through the breaking of the Cl-S single bond, giving a chloride radical and a SO2NCO+ fragment. This mechanism contrasts with the one observed for the related FSO2NCO, in which the rupture of the S-N bond originates the FSO2+ fragment. The energies of the shallow- (S 2p, Cl 2p, and S 2s) and core-shell (C 1s, N 1s, and O 1s) electrons were determined by X-ray absorption. Transitions between these shallow and core electrons to unoccupied molecular orbitals were also observed in the total ion yield (TIY) spectra. Fourteen different fragmentation mechanisms of the doubly charged parent ion, ClSO2NCO2+, were inferred from the bidimensional photoelectron-photoion-photoion-coincidence (PEPIPICO) spectra. The rupture of the S-N bond can evolve to form NCO+/SO2•+, NCO+/SO•+, or S•+/NCO+ pairs of ions. The Cl-S bond breaking originates different mechanisms, Cl+/SO•+, Cl+/S•+, CO•+/S•+, O•+/SO•+, O•+/Cl+, O•+/S•+, C•+/S•+, and C•+/O•+ pairs being detected in coincidence as the final species. Another three coincidence islands can only be explained with an initial atomic rearrangement forming ClNCO2+, ONCO2+, and ClCO2+, as precursors of CO•+/Cl+, O•+/CO•+, and C•+/Cl+ pairs, respectively. The formation of Cl• radical is deduced from several mechanisms. (Figure Presented).
publishDate 2015
dc.date.none.fl_str_mv 2015-07
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
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info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/65858
Moreno Betancourt, Angelica; Bava, Yanina Belén; Berrueta Martinez, Yanina; Erben, Mauricio Federico; Cavasso Filho Reinaldo L.; et al.; Photofragmentation Mechanisms of Chlorosulfonyl Isocyanate, ClSO2NCO, Excited with Synchrotron Radiation between 12 and 550 eV; American Chemical Society; Journal of Physical Chemistry A; 119; 29; 7-2015; 8021-8030
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/65858
identifier_str_mv Moreno Betancourt, Angelica; Bava, Yanina Belén; Berrueta Martinez, Yanina; Erben, Mauricio Federico; Cavasso Filho Reinaldo L.; et al.; Photofragmentation Mechanisms of Chlorosulfonyl Isocyanate, ClSO2NCO, Excited with Synchrotron Radiation between 12 and 550 eV; American Chemical Society; Journal of Physical Chemistry A; 119; 29; 7-2015; 8021-8030
1089-5639
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/acs.jpca.5b02396
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.5b02396
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
application/pdf
application/pdf
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
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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