Conformational cooling and conformation selective aggregation in dimethyl sulfite isolated in solid rare gases

Autores
Borba, Ana; Gomez Zavaglia, Andrea; Fausto, Rui
Año de publicación
2006
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Dimethyl sulfite has three conformers of low energy, GG, GT and GG0 , which have significant populations in the gas phase at room temperature. According to theoretical predictions, the GT and GG0 conformers are higher in energy than the GG conformer by 0.83 and 1.18 kJ molK1 , respectively, while the barriers associated with the GG0 /GT and GT/GG isomerizations are 1.90 and 9.64 kJ molK1 , respectively. Experimental data obtained for the compound isolated in solid argon, krypton and xenon demonstrated that the GG0 /GT energy barrier is low enough to allow an extensive conversion of the GG0 form into the GT conformer during deposition of the matrices, the extent of the conversion increasing along the series Ar!Kr!Xe. Indeed, for substrate temperatures lower than ca. 30 K, the three conformers could be trapped in both argon and krypton matrices, but, at a given temperature, the amount of GG0 form trapped in krypton is considerably smaller than in argon, while the amount of GT form increases in relation to the most stable GG form. In addition, when xenon is used, no bands due to GG0 are observed in the as-deposited spectra (TsubstrateR10 K, the minimum substrate temperature accessible to our experimental set up), indicating that when the best relaxant gas is used the GG0 /GT conversion during deposition of the matrix is complete even at 10 K. Annealing of the argon and krypton matrices shows that the increase of the temperature of the matrix first promotes the GG0 /GT isomerization, and only at higher temperatures the GT/GG conversion starts to occur, in consonance with the relative energy barriers associated with these two processes. The results also indicate that dimethyl sulfite exhibits conformation selective aggregation, with the most stable form, which has the highest dipole moment, aggregating more easily than the remaining experimentally relevant conformers (GT and GG0).
Fil: Borba, Ana. Universidad de Coimbra; Portugal
Fil: Gomez Zavaglia, Andrea. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Universidad de Coimbra; Portugal. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; Argentina
Fil: Fausto, Rui. Universidad de Coimbra; Portugal
Materia
Matrix isolation FTIR Spectroscopy
Dimethyl sulfite
Conformational cooling
Conformation selective aggregation
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:11336/116104
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/116104
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Conformational cooling and conformation selective aggregation in dimethyl sulfite isolated in solid rare gasesBorba, AnaGomez Zavaglia, AndreaFausto, RuiMatrix isolation FTIR SpectroscopyDimethyl sulfiteConformational coolingConformation selective aggregationhttps://purl.org/becyt/ford/2.11https://purl.org/becyt/ford/2Dimethyl sulfite has three conformers of low energy, GG, GT and GG0 , which have significant populations in the gas phase at room temperature. According to theoretical predictions, the GT and GG0 conformers are higher in energy than the GG conformer by 0.83 and 1.18 kJ molK1 , respectively, while the barriers associated with the GG0 /GT and GT/GG isomerizations are 1.90 and 9.64 kJ molK1 , respectively. Experimental data obtained for the compound isolated in solid argon, krypton and xenon demonstrated that the GG0 /GT energy barrier is low enough to allow an extensive conversion of the GG0 form into the GT conformer during deposition of the matrices, the extent of the conversion increasing along the series Ar!Kr!Xe. Indeed, for substrate temperatures lower than ca. 30 K, the three conformers could be trapped in both argon and krypton matrices, but, at a given temperature, the amount of GG0 form trapped in krypton is considerably smaller than in argon, while the amount of GT form increases in relation to the most stable GG form. In addition, when xenon is used, no bands due to GG0 are observed in the as-deposited spectra (TsubstrateR10 K, the minimum substrate temperature accessible to our experimental set up), indicating that when the best relaxant gas is used the GG0 /GT conversion during deposition of the matrix is complete even at 10 K. Annealing of the argon and krypton matrices shows that the increase of the temperature of the matrix first promotes the GG0 /GT isomerization, and only at higher temperatures the GT/GG conversion starts to occur, in consonance with the relative energy barriers associated with these two processes. The results also indicate that dimethyl sulfite exhibits conformation selective aggregation, with the most stable form, which has the highest dipole moment, aggregating more easily than the remaining experimentally relevant conformers (GT and GG0).Fil: Borba, Ana. Universidad de Coimbra; PortugalFil: Gomez Zavaglia, Andrea. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Universidad de Coimbra; Portugal. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; ArgentinaFil: Fausto, Rui. Universidad de Coimbra; PortugalElsevier Science2006-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/116104Borba, Ana; Gomez Zavaglia, Andrea; Fausto, Rui; Conformational cooling and conformation selective aggregation in dimethyl sulfite isolated in solid rare gases; Elsevier Science; Journal of Molecular Structure; 794; 1-3; 8-2006; 196-2030022-28601872-8014CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://tinyurl.com/y6eskl3cinfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.molstruc.2006.02.005info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T12:19:39Zoai:ri.conicet.gov.ar:11336/116104instacron: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:34982025-10-22 12:19:39.414CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Conformational cooling and conformation selective aggregation in dimethyl sulfite isolated in solid rare gases
title Conformational cooling and conformation selective aggregation in dimethyl sulfite isolated in solid rare gases
spellingShingle Conformational cooling and conformation selective aggregation in dimethyl sulfite isolated in solid rare gases
Borba, Ana
Matrix isolation FTIR Spectroscopy
Dimethyl sulfite
Conformational cooling
Conformation selective aggregation
title_short Conformational cooling and conformation selective aggregation in dimethyl sulfite isolated in solid rare gases
title_full Conformational cooling and conformation selective aggregation in dimethyl sulfite isolated in solid rare gases
title_fullStr Conformational cooling and conformation selective aggregation in dimethyl sulfite isolated in solid rare gases
title_full_unstemmed Conformational cooling and conformation selective aggregation in dimethyl sulfite isolated in solid rare gases
title_sort Conformational cooling and conformation selective aggregation in dimethyl sulfite isolated in solid rare gases
dc.creator.none.fl_str_mv Borba, Ana
Gomez Zavaglia, Andrea
Fausto, Rui
author Borba, Ana
author_facet Borba, Ana
Gomez Zavaglia, Andrea
Fausto, Rui
author_role author
author2 Gomez Zavaglia, Andrea
Fausto, Rui
author2_role author
author
dc.subject.none.fl_str_mv Matrix isolation FTIR Spectroscopy
Dimethyl sulfite
Conformational cooling
Conformation selective aggregation
topic Matrix isolation FTIR Spectroscopy
Dimethyl sulfite
Conformational cooling
Conformation selective aggregation
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.11
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv Dimethyl sulfite has three conformers of low energy, GG, GT and GG0 , which have significant populations in the gas phase at room temperature. According to theoretical predictions, the GT and GG0 conformers are higher in energy than the GG conformer by 0.83 and 1.18 kJ molK1 , respectively, while the barriers associated with the GG0 /GT and GT/GG isomerizations are 1.90 and 9.64 kJ molK1 , respectively. Experimental data obtained for the compound isolated in solid argon, krypton and xenon demonstrated that the GG0 /GT energy barrier is low enough to allow an extensive conversion of the GG0 form into the GT conformer during deposition of the matrices, the extent of the conversion increasing along the series Ar!Kr!Xe. Indeed, for substrate temperatures lower than ca. 30 K, the three conformers could be trapped in both argon and krypton matrices, but, at a given temperature, the amount of GG0 form trapped in krypton is considerably smaller than in argon, while the amount of GT form increases in relation to the most stable GG form. In addition, when xenon is used, no bands due to GG0 are observed in the as-deposited spectra (TsubstrateR10 K, the minimum substrate temperature accessible to our experimental set up), indicating that when the best relaxant gas is used the GG0 /GT conversion during deposition of the matrix is complete even at 10 K. Annealing of the argon and krypton matrices shows that the increase of the temperature of the matrix first promotes the GG0 /GT isomerization, and only at higher temperatures the GT/GG conversion starts to occur, in consonance with the relative energy barriers associated with these two processes. The results also indicate that dimethyl sulfite exhibits conformation selective aggregation, with the most stable form, which has the highest dipole moment, aggregating more easily than the remaining experimentally relevant conformers (GT and GG0).
Fil: Borba, Ana. Universidad de Coimbra; Portugal
Fil: Gomez Zavaglia, Andrea. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Universidad de Coimbra; Portugal. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; Argentina
Fil: Fausto, Rui. Universidad de Coimbra; Portugal
description Dimethyl sulfite has three conformers of low energy, GG, GT and GG0 , which have significant populations in the gas phase at room temperature. According to theoretical predictions, the GT and GG0 conformers are higher in energy than the GG conformer by 0.83 and 1.18 kJ molK1 , respectively, while the barriers associated with the GG0 /GT and GT/GG isomerizations are 1.90 and 9.64 kJ molK1 , respectively. Experimental data obtained for the compound isolated in solid argon, krypton and xenon demonstrated that the GG0 /GT energy barrier is low enough to allow an extensive conversion of the GG0 form into the GT conformer during deposition of the matrices, the extent of the conversion increasing along the series Ar!Kr!Xe. Indeed, for substrate temperatures lower than ca. 30 K, the three conformers could be trapped in both argon and krypton matrices, but, at a given temperature, the amount of GG0 form trapped in krypton is considerably smaller than in argon, while the amount of GT form increases in relation to the most stable GG form. In addition, when xenon is used, no bands due to GG0 are observed in the as-deposited spectra (TsubstrateR10 K, the minimum substrate temperature accessible to our experimental set up), indicating that when the best relaxant gas is used the GG0 /GT conversion during deposition of the matrix is complete even at 10 K. Annealing of the argon and krypton matrices shows that the increase of the temperature of the matrix first promotes the GG0 /GT isomerization, and only at higher temperatures the GT/GG conversion starts to occur, in consonance with the relative energy barriers associated with these two processes. The results also indicate that dimethyl sulfite exhibits conformation selective aggregation, with the most stable form, which has the highest dipole moment, aggregating more easily than the remaining experimentally relevant conformers (GT and GG0).
publishDate 2006
dc.date.none.fl_str_mv 2006-08
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/11336/116104
Borba, Ana; Gomez Zavaglia, Andrea; Fausto, Rui; Conformational cooling and conformation selective aggregation in dimethyl sulfite isolated in solid rare gases; Elsevier Science; Journal of Molecular Structure; 794; 1-3; 8-2006; 196-203
0022-2860
1872-8014
CONICET Digital
CONICET
url http://hdl.handle.net/11336/116104
identifier_str_mv Borba, Ana; Gomez Zavaglia, Andrea; Fausto, Rui; Conformational cooling and conformation selective aggregation in dimethyl sulfite isolated in solid rare gases; Elsevier Science; Journal of Molecular Structure; 794; 1-3; 8-2006; 196-203
0022-2860
1872-8014
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://tinyurl.com/y6eskl3c
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.molstruc.2006.02.005
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
dc.publisher.none.fl_str_mv Elsevier Science
publisher.none.fl_str_mv Elsevier Science
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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score 13.144186

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