New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with ga...
- Autores
- Tamone, Luciana Mariel; Picone, Andrea Lorena; Romano, Rosana Mariel
- Año de publicación
- 2021
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- Photolysis products of dichloroacetyl chloride (DCAC) isolated in Ar matrix and in gas phase, in the absence and presence of molecular oxygen, were studied by means of FTIR spectroscopy. The samples were exposed to light of different energy ranges (200-800, 280-320, 350-450 and 400-800 nm). DCAC is photostable when irradiated with light of wavelengths above 400 nm, and gives dichloroketene after photolysis with light between 280-320 and 350-450 nm. Exposure of DCAC to broad-band radiation (200-800 nm) produces dichloroketene as an intermediate photoproduct, and different 1:1 CHCl3:CO molecular complexes after further irradiation. HCl, CO and CHCl3 were detected in gas-phase DCAC photolysis. ClC(O)CCl2CCl2H molecule was also proposed, in a mechanism that involve the insertion of :CCl2 biradical into the CC bond of DCAC. The photochemical reaction of DCAC with O2 in Ar matrix gives Cl2CO and CO2. The same photoproducts, together with HCl, were observed in the gas-phase photochemical reaction. Additionally, the FTIR spectra of DCAC isolated in solid Ar were fully interpreted in terms of an equilibrium between syn (the HC bond syn with respect to the CO bond) and gauche conformers. Some absorptions, which grow as the DCAC:Ar ratio increases, were attributed to dimeric forms. The most stable dimer was predicted by DFT calculations as composed by two DCAC molecules with syn conformations, interacting through two H-bonds in a structure with Ci symmetry.
Centro de Química Inorgánica - Materia
-
Química
Dichloroacetyl chloride
Matrix-isolation
Photochemistry
IR spectroscopy
Dimers - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- http://creativecommons.org/licenses/by-nc-nd/4.0/
- Repositorio
- Institución
- Universidad Nacional de La Plata
- OAI Identificador
- oai:sedici.unlp.edu.ar:10915/112819
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New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistryTamone, Luciana MarielPicone, Andrea LorenaRomano, Rosana MarielQuímicaDichloroacetyl chlorideMatrix-isolationPhotochemistryIR spectroscopyDimersPhotolysis products of dichloroacetyl chloride (DCAC) isolated in Ar matrix and in gas phase, in the absence and presence of molecular oxygen, were studied by means of FTIR spectroscopy. The samples were exposed to light of different energy ranges (200-800, 280-320, 350-450 and 400-800 nm). DCAC is photostable when irradiated with light of wavelengths above 400 nm, and gives dichloroketene after photolysis with light between 280-320 and 350-450 nm. Exposure of DCAC to broad-band radiation (200-800 nm) produces dichloroketene as an intermediate photoproduct, and different 1:1 CHCl3:CO molecular complexes after further irradiation. HCl, CO and CHCl3 were detected in gas-phase DCAC photolysis. ClC(O)CCl2CCl2H molecule was also proposed, in a mechanism that involve the insertion of :CCl2 biradical into the CC bond of DCAC. The photochemical reaction of DCAC with O2 in Ar matrix gives Cl2CO and CO2. The same photoproducts, together with HCl, were observed in the gas-phase photochemical reaction. Additionally, the FTIR spectra of DCAC isolated in solid Ar were fully interpreted in terms of an equilibrium between syn (the HC bond syn with respect to the CO bond) and gauche conformers. Some absorptions, which grow as the DCAC:Ar ratio increases, were attributed to dimeric forms. The most stable dimer was predicted by DFT calculations as composed by two DCAC molecules with syn conformations, interacting through two H-bonds in a structure with Ci symmetry.Centro de Química Inorgánica2021-01-29info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfhttp://sedici.unlp.edu.ar/handle/10915/112819enginfo:eu-repo/semantics/altIdentifier/issn/2666-4690info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jpap.2021.100019info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-nd/4.0/Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-09-03T10:58:06Zoai:sedici.unlp.edu.ar:10915/112819Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-03 10:58:06.776SEDICI (UNLP) - Universidad Nacional de La Platafalse |
dc.title.none.fl_str_mv |
New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry |
title |
New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry |
spellingShingle |
New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry Tamone, Luciana Mariel Química Dichloroacetyl chloride Matrix-isolation Photochemistry IR spectroscopy Dimers |
title_short |
New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry |
title_full |
New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry |
title_fullStr |
New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry |
title_full_unstemmed |
New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry |
title_sort |
New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry |
dc.creator.none.fl_str_mv |
Tamone, Luciana Mariel Picone, Andrea Lorena Romano, Rosana Mariel |
author |
Tamone, Luciana Mariel |
author_facet |
Tamone, Luciana Mariel Picone, Andrea Lorena Romano, Rosana Mariel |
author_role |
author |
author2 |
Picone, Andrea Lorena Romano, Rosana Mariel |
author2_role |
author author |
dc.subject.none.fl_str_mv |
Química Dichloroacetyl chloride Matrix-isolation Photochemistry IR spectroscopy Dimers |
topic |
Química Dichloroacetyl chloride Matrix-isolation Photochemistry IR spectroscopy Dimers |
dc.description.none.fl_txt_mv |
Photolysis products of dichloroacetyl chloride (DCAC) isolated in Ar matrix and in gas phase, in the absence and presence of molecular oxygen, were studied by means of FTIR spectroscopy. The samples were exposed to light of different energy ranges (200-800, 280-320, 350-450 and 400-800 nm). DCAC is photostable when irradiated with light of wavelengths above 400 nm, and gives dichloroketene after photolysis with light between 280-320 and 350-450 nm. Exposure of DCAC to broad-band radiation (200-800 nm) produces dichloroketene as an intermediate photoproduct, and different 1:1 CHCl3:CO molecular complexes after further irradiation. HCl, CO and CHCl3 were detected in gas-phase DCAC photolysis. ClC(O)CCl2CCl2H molecule was also proposed, in a mechanism that involve the insertion of :CCl2 biradical into the CC bond of DCAC. The photochemical reaction of DCAC with O2 in Ar matrix gives Cl2CO and CO2. The same photoproducts, together with HCl, were observed in the gas-phase photochemical reaction. Additionally, the FTIR spectra of DCAC isolated in solid Ar were fully interpreted in terms of an equilibrium between syn (the HC bond syn with respect to the CO bond) and gauche conformers. Some absorptions, which grow as the DCAC:Ar ratio increases, were attributed to dimeric forms. The most stable dimer was predicted by DFT calculations as composed by two DCAC molecules with syn conformations, interacting through two H-bonds in a structure with Ci symmetry. Centro de Química Inorgánica |
description |
Photolysis products of dichloroacetyl chloride (DCAC) isolated in Ar matrix and in gas phase, in the absence and presence of molecular oxygen, were studied by means of FTIR spectroscopy. The samples were exposed to light of different energy ranges (200-800, 280-320, 350-450 and 400-800 nm). DCAC is photostable when irradiated with light of wavelengths above 400 nm, and gives dichloroketene after photolysis with light between 280-320 and 350-450 nm. Exposure of DCAC to broad-band radiation (200-800 nm) produces dichloroketene as an intermediate photoproduct, and different 1:1 CHCl3:CO molecular complexes after further irradiation. HCl, CO and CHCl3 were detected in gas-phase DCAC photolysis. ClC(O)CCl2CCl2H molecule was also proposed, in a mechanism that involve the insertion of :CCl2 biradical into the CC bond of DCAC. The photochemical reaction of DCAC with O2 in Ar matrix gives Cl2CO and CO2. The same photoproducts, together with HCl, were observed in the gas-phase photochemical reaction. Additionally, the FTIR spectra of DCAC isolated in solid Ar were fully interpreted in terms of an equilibrium between syn (the HC bond syn with respect to the CO bond) and gauche conformers. Some absorptions, which grow as the DCAC:Ar ratio increases, were attributed to dimeric forms. The most stable dimer was predicted by DFT calculations as composed by two DCAC molecules with syn conformations, interacting through two H-bonds in a structure with Ci symmetry. |
publishDate |
2021 |
dc.date.none.fl_str_mv |
2021-01-29 |
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/10915/112819 |
url |
http://sedici.unlp.edu.ar/handle/10915/112819 |
dc.language.none.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
info:eu-repo/semantics/altIdentifier/issn/2666-4690 info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jpap.2021.100019 |
dc.rights.none.fl_str_mv |
info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by-nc-nd/4.0/ Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) |
eu_rights_str_mv |
openAccess |
rights_invalid_str_mv |
http://creativecommons.org/licenses/by-nc-nd/4.0/ Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) |
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