Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2...

Autores
Rodríguez Pirani, Lucas; Della Védova, Carlos Omar; Geronés, Mariana; Romano, Rosana Mariel; Cavasso Filho, Reinaldo; Ge, Maofa; Ma, Chunping; Erben, Mauricio Federico
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Both photoelectron spectroscopy (PES) data and PhotoElectron-PhotoIon-Coincidence (PEPICO) spectra obtained from a synchrotron facility have been used to examine the electronic structure and the dissociative ionization of halomethyl thiocyantes in the valence and shallow-core S 2p and Cl 2pregions. Two simple and closely related molecules, namely, CCl3SCN and CCl2FSCN, have been analyzed to assess the role of halogen substitution in the electronic properties of thiocyanates. The assignment of the He(I) photoelectron spectra has been achieved with the help of quantum chemical calculations at the outer-valence Green’s function (OVGF) level of approximation. The first ionization energies observed at 10.55 and 10.78 eV for CCl3SCN and CCl2FSCN, respectively, are assigned to ionization processes from the sulfur lone pair orbital [n(S)]. When these molecules are compared with CX3SCN (X = H, Cl, F) species, a linear relationship between the vertical first ionization energy and electronegativity of CX3 group is observed. Irradiation of CCl3SCN and CCl2FSCN with photons in the valence energy regions leads to the formation of CCl2X⁺ and CClXSCN⁺ ions (X = Cl or F). Additionally, the achievement of the fragmentation patterns and the total ion yield spectra obtained from the PEPICO data in the S 2p and Cl 2p regions and several dissociation channels can be inferred for the core-excited species by using the triple coincidence PEPIPICO (PhotoElectron-PhotoIon-PhotoIon-Coincidence) spectra.
Facultad de Ciencias Exactas
Centro de Química Inorgánica
Materia
Ciencias Exactas
Química
Thiocyanates
electronic structure
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by-nc-sa/4.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/107184
Acceder
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oai_identifier_str oai:sedici.unlp.edu.ar:10915/107184
network_acronym_str SEDICI
repository_id_str 1329
network_name_str SEDICI (UNLP)
spelling Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCNRodríguez Pirani, LucasDella Védova, Carlos OmarGeronés, MarianaRomano, Rosana MarielCavasso Filho, ReinaldoGe, MaofaMa, ChunpingErben, Mauricio FedericoCiencias ExactasQuímicaThiocyanateselectronic structureBoth photoelectron spectroscopy (PES) data and PhotoElectron-PhotoIon-Coincidence (PEPICO) spectra obtained from a synchrotron facility have been used to examine the electronic structure and the dissociative ionization of halomethyl thiocyantes in the valence and shallow-core S 2p and Cl 2pregions. Two simple and closely related molecules, namely, CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN, have been analyzed to assess the role of halogen substitution in the electronic properties of thiocyanates. The assignment of the He(I) photoelectron spectra has been achieved with the help of quantum chemical calculations at the outer-valence Green’s function (OVGF) level of approximation. The first ionization energies observed at 10.55 and 10.78 eV for CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN, respectively, are assigned to ionization processes from the sulfur lone pair orbital [n(S)]. When these molecules are compared with CX<sub>3</sub>SCN (X = H, Cl, F) species, a linear relationship between the vertical first ionization energy and electronegativity of CX<sub>3</sub> group is observed. Irradiation of CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN with photons in the valence energy regions leads to the formation of CCl<sub>2</sub>X⁺ and CClXSCN⁺ ions (X = Cl or F). Additionally, the achievement of the fragmentation patterns and the total ion yield spectra obtained from the PEPICO data in the S 2p and Cl 2p regions and several dissociation channels can be inferred for the core-excited species by using the triple coincidence PEPIPICO (PhotoElectron-PhotoIon-PhotoIon-Coincidence) spectra.Facultad de Ciencias ExactasCentro de Química Inorgánica2017info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf9201-9210http://sedici.unlp.edu.ar/handle/10915/107184enginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpca.7b08395info:eu-repo/semantics/altIdentifier/issn/1520-5215info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.7b08395info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-sa/4.0/Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-09-29T11:24:01Zoai:sedici.unlp.edu.ar:10915/107184Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-29 11:24:01.98SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN
title Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN
spellingShingle Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN
Rodríguez Pirani, Lucas
Ciencias Exactas
Química
Thiocyanates
electronic structure
title_short Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN
title_full Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN
title_fullStr Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN
title_full_unstemmed Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN
title_sort Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN
dc.creator.none.fl_str_mv Rodríguez Pirani, Lucas
Della Védova, Carlos Omar
Geronés, Mariana
Romano, Rosana Mariel
Cavasso Filho, Reinaldo
Ge, Maofa
Ma, Chunping
Erben, Mauricio Federico
author Rodríguez Pirani, Lucas
author_facet Rodríguez Pirani, Lucas
Della Védova, Carlos Omar
Geronés, Mariana
Romano, Rosana Mariel
Cavasso Filho, Reinaldo
Ge, Maofa
Ma, Chunping
Erben, Mauricio Federico
author_role author
author2 Della Védova, Carlos Omar
Geronés, Mariana
Romano, Rosana Mariel
Cavasso Filho, Reinaldo
Ge, Maofa
Ma, Chunping
Erben, Mauricio Federico
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Ciencias Exactas
Química
Thiocyanates
electronic structure
topic Ciencias Exactas
Química
Thiocyanates
electronic structure
dc.description.none.fl_txt_mv Both photoelectron spectroscopy (PES) data and PhotoElectron-PhotoIon-Coincidence (PEPICO) spectra obtained from a synchrotron facility have been used to examine the electronic structure and the dissociative ionization of halomethyl thiocyantes in the valence and shallow-core S 2p and Cl 2pregions. Two simple and closely related molecules, namely, CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN, have been analyzed to assess the role of halogen substitution in the electronic properties of thiocyanates. The assignment of the He(I) photoelectron spectra has been achieved with the help of quantum chemical calculations at the outer-valence Green’s function (OVGF) level of approximation. The first ionization energies observed at 10.55 and 10.78 eV for CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN, respectively, are assigned to ionization processes from the sulfur lone pair orbital [n(S)]. When these molecules are compared with CX<sub>3</sub>SCN (X = H, Cl, F) species, a linear relationship between the vertical first ionization energy and electronegativity of CX<sub>3</sub> group is observed. Irradiation of CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN with photons in the valence energy regions leads to the formation of CCl<sub>2</sub>X⁺ and CClXSCN⁺ ions (X = Cl or F). Additionally, the achievement of the fragmentation patterns and the total ion yield spectra obtained from the PEPICO data in the S 2p and Cl 2p regions and several dissociation channels can be inferred for the core-excited species by using the triple coincidence PEPIPICO (PhotoElectron-PhotoIon-PhotoIon-Coincidence) spectra.
Facultad de Ciencias Exactas
Centro de Química Inorgánica
description Both photoelectron spectroscopy (PES) data and PhotoElectron-PhotoIon-Coincidence (PEPICO) spectra obtained from a synchrotron facility have been used to examine the electronic structure and the dissociative ionization of halomethyl thiocyantes in the valence and shallow-core S 2p and Cl 2pregions. Two simple and closely related molecules, namely, CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN, have been analyzed to assess the role of halogen substitution in the electronic properties of thiocyanates. The assignment of the He(I) photoelectron spectra has been achieved with the help of quantum chemical calculations at the outer-valence Green’s function (OVGF) level of approximation. The first ionization energies observed at 10.55 and 10.78 eV for CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN, respectively, are assigned to ionization processes from the sulfur lone pair orbital [n(S)]. When these molecules are compared with CX<sub>3</sub>SCN (X = H, Cl, F) species, a linear relationship between the vertical first ionization energy and electronegativity of CX<sub>3</sub> group is observed. Irradiation of CCl<sub>3</sub>SCN and CCl<sub>2</sub>FSCN with photons in the valence energy regions leads to the formation of CCl<sub>2</sub>X⁺ and CClXSCN⁺ ions (X = Cl or F). Additionally, the achievement of the fragmentation patterns and the total ion yield spectra obtained from the PEPICO data in the S 2p and Cl 2p regions and several dissociation channels can be inferred for the core-excited species by using the triple coincidence PEPIPICO (PhotoElectron-PhotoIon-PhotoIon-Coincidence) spectra.
publishDate 2017
dc.date.none.fl_str_mv 2017
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
Articulo
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://sedici.unlp.edu.ar/handle/10915/107184
url http://sedici.unlp.edu.ar/handle/10915/107184
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpca.7b08395
info:eu-repo/semantics/altIdentifier/issn/1520-5215
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.7b08395
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
dc.format.none.fl_str_mv application/pdf
9201-9210
dc.source.none.fl_str_mv reponame:SEDICI (UNLP)
instname:Universidad Nacional de La Plata
instacron:UNLP
reponame_str SEDICI (UNLP)
collection SEDICI (UNLP)
instname_str Universidad Nacional de La Plata
instacron_str UNLP
institution UNLP
repository.name.fl_str_mv SEDICI (UNLP) - Universidad Nacional de La Plata
repository.mail.fl_str_mv alira@sedici.unlp.edu.ar
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score 13.069144

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