Quantum chemical characterization of the CF2(OH)CF2OONO2 and CF3CF2OONO2 peroxynitrates and related radicals

Autores
Delvalle Mongelós, Rosa Isabel; Badenes, Maria Paula
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We present a detailed study of the molecular conformations, vibrational spectra and thermochemistry of the CF2(OH)CF2OONO2 and CF3CF2OONO2 peroxynitrates. In addition, we studied the CF2(OH)CF2OO, CF2(OH)CF2O, CF3CF2OO and CF3CF2O radicals, formed by the rupture of Osingle bondN and Osingle bondO bonds of the above peroxynitrates. The geometric structures of the most stable conformations were determined by density functional theory calculations. At the B3LYP/6-311++G(3df,3pd) level of theory, both peroxynitrates present dihedral angle COON values of about 104°. At the best levels of theory employed, G3(MP2)B3 and G4(MP2), the standard enthalpies of formation at 298 K derived from isodesmic reactions, are −265.6, −248.6 and −248.5 kcal mol−1 for CF2(OH)CF2OONO2, CF2(OH)CF2OO and CF2(OH)CF2O respectively; while for CF3CF2OONO2, CF3CF2OO and CF3CF2O the values of −268.2, −252.6 and −251.9 kcal mol−1 were obtained. Bond dissociation enthalpies of 25.1 and 35.0 kcal mol−1 have been predicted for the first time for CF2(OH)CF2OOsingle bondNO2 and CF2(OH)CF2Osingle bondONO2 and of 23.7 and 34.2 kcal mol−1 have been estimated for CF3CF2OOsingle bondNO2 and CF3CF2Osingle bondONO2. The obtained result of the dissociation enthalpy of CF3CF2OOsingle bondNO2 is in excellent agreement with the available experimental determination. Therefore, the Osingle bondN bond fission is the primary thermal dissociation pathway for both studied peroxynitrates.
Fil: Delvalle Mongelós, Rosa Isabel. Universidad Nacional de Asuncion; Paraguay
Fil: Badenes, Maria Paula. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de la Plata; Argentina
Materia
Cf2(Oh)Cf2oono2
Cf3cf2oono2
Fluorinated Peroxynitrates
Quantum-Chemical Calculations
Enthalpy of Formation
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/5082
Acceder
id CONICETDig_a8d24bfc55d166e925a13d5518171dd3
oai_identifier_str oai:ri.conicet.gov.ar:11336/5082
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Quantum chemical characterization of the CF2(OH)CF2OONO2 and CF3CF2OONO2 peroxynitrates and related radicalsDelvalle Mongelós, Rosa IsabelBadenes, Maria PaulaCf2(Oh)Cf2oono2Cf3cf2oono2Fluorinated PeroxynitratesQuantum-Chemical CalculationsEnthalpy of Formationhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We present a detailed study of the molecular conformations, vibrational spectra and thermochemistry of the CF2(OH)CF2OONO2 and CF3CF2OONO2 peroxynitrates. In addition, we studied the CF2(OH)CF2OO, CF2(OH)CF2O, CF3CF2OO and CF3CF2O radicals, formed by the rupture of Osingle bondN and Osingle bondO bonds of the above peroxynitrates. The geometric structures of the most stable conformations were determined by density functional theory calculations. At the B3LYP/6-311++G(3df,3pd) level of theory, both peroxynitrates present dihedral angle COON values of about 104°. At the best levels of theory employed, G3(MP2)B3 and G4(MP2), the standard enthalpies of formation at 298 K derived from isodesmic reactions, are −265.6, −248.6 and −248.5 kcal mol−1 for CF2(OH)CF2OONO2, CF2(OH)CF2OO and CF2(OH)CF2O respectively; while for CF3CF2OONO2, CF3CF2OO and CF3CF2O the values of −268.2, −252.6 and −251.9 kcal mol−1 were obtained. Bond dissociation enthalpies of 25.1 and 35.0 kcal mol−1 have been predicted for the first time for CF2(OH)CF2OOsingle bondNO2 and CF2(OH)CF2Osingle bondONO2 and of 23.7 and 34.2 kcal mol−1 have been estimated for CF3CF2OOsingle bondNO2 and CF3CF2Osingle bondONO2. The obtained result of the dissociation enthalpy of CF3CF2OOsingle bondNO2 is in excellent agreement with the available experimental determination. Therefore, the Osingle bondN bond fission is the primary thermal dissociation pathway for both studied peroxynitrates.Fil: Delvalle Mongelós, Rosa Isabel. Universidad Nacional de Asuncion; ParaguayFil: Badenes, Maria Paula. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de la Plata; ArgentinaElsevier2015-04info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/5082Delvalle Mongelós, Rosa Isabel; Badenes, Maria Paula; Quantum chemical characterization of the CF2(OH)CF2OONO2 and CF3CF2OONO2 peroxynitrates and related radicals; Elsevier; Computational and Theoretical Chemistry; 1062; 4-2015; 65-732210-271Xenginfo:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S2210271X15001395info:eu-repo/semantics/altIdentifier/doi/info:eu-repo/semantics/altIdentifier/doi/10.1016/j.comptc.2015.03.024info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:09:06Zoai:ri.conicet.gov.ar:11336/5082instacron: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 10:09:07.27CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Quantum chemical characterization of the CF2(OH)CF2OONO2 and CF3CF2OONO2 peroxynitrates and related radicals
title Quantum chemical characterization of the CF2(OH)CF2OONO2 and CF3CF2OONO2 peroxynitrates and related radicals
spellingShingle Quantum chemical characterization of the CF2(OH)CF2OONO2 and CF3CF2OONO2 peroxynitrates and related radicals
Delvalle Mongelós, Rosa Isabel
Cf2(Oh)Cf2oono2
Cf3cf2oono2
Fluorinated Peroxynitrates
Quantum-Chemical Calculations
Enthalpy of Formation
title_short Quantum chemical characterization of the CF2(OH)CF2OONO2 and CF3CF2OONO2 peroxynitrates and related radicals
title_full Quantum chemical characterization of the CF2(OH)CF2OONO2 and CF3CF2OONO2 peroxynitrates and related radicals
title_fullStr Quantum chemical characterization of the CF2(OH)CF2OONO2 and CF3CF2OONO2 peroxynitrates and related radicals
title_full_unstemmed Quantum chemical characterization of the CF2(OH)CF2OONO2 and CF3CF2OONO2 peroxynitrates and related radicals
title_sort Quantum chemical characterization of the CF2(OH)CF2OONO2 and CF3CF2OONO2 peroxynitrates and related radicals
dc.creator.none.fl_str_mv Delvalle Mongelós, Rosa Isabel
Badenes, Maria Paula
author Delvalle Mongelós, Rosa Isabel
author_facet Delvalle Mongelós, Rosa Isabel
Badenes, Maria Paula
author_role author
author2 Badenes, Maria Paula
author2_role author
dc.subject.none.fl_str_mv Cf2(Oh)Cf2oono2
Cf3cf2oono2
Fluorinated Peroxynitrates
Quantum-Chemical Calculations
Enthalpy of Formation
topic Cf2(Oh)Cf2oono2
Cf3cf2oono2
Fluorinated Peroxynitrates
Quantum-Chemical Calculations
Enthalpy of Formation
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We present a detailed study of the molecular conformations, vibrational spectra and thermochemistry of the CF2(OH)CF2OONO2 and CF3CF2OONO2 peroxynitrates. In addition, we studied the CF2(OH)CF2OO, CF2(OH)CF2O, CF3CF2OO and CF3CF2O radicals, formed by the rupture of Osingle bondN and Osingle bondO bonds of the above peroxynitrates. The geometric structures of the most stable conformations were determined by density functional theory calculations. At the B3LYP/6-311++G(3df,3pd) level of theory, both peroxynitrates present dihedral angle COON values of about 104°. At the best levels of theory employed, G3(MP2)B3 and G4(MP2), the standard enthalpies of formation at 298 K derived from isodesmic reactions, are −265.6, −248.6 and −248.5 kcal mol−1 for CF2(OH)CF2OONO2, CF2(OH)CF2OO and CF2(OH)CF2O respectively; while for CF3CF2OONO2, CF3CF2OO and CF3CF2O the values of −268.2, −252.6 and −251.9 kcal mol−1 were obtained. Bond dissociation enthalpies of 25.1 and 35.0 kcal mol−1 have been predicted for the first time for CF2(OH)CF2OOsingle bondNO2 and CF2(OH)CF2Osingle bondONO2 and of 23.7 and 34.2 kcal mol−1 have been estimated for CF3CF2OOsingle bondNO2 and CF3CF2Osingle bondONO2. The obtained result of the dissociation enthalpy of CF3CF2OOsingle bondNO2 is in excellent agreement with the available experimental determination. Therefore, the Osingle bondN bond fission is the primary thermal dissociation pathway for both studied peroxynitrates.
Fil: Delvalle Mongelós, Rosa Isabel. Universidad Nacional de Asuncion; Paraguay
Fil: Badenes, Maria Paula. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de la Plata; Argentina
description We present a detailed study of the molecular conformations, vibrational spectra and thermochemistry of the CF2(OH)CF2OONO2 and CF3CF2OONO2 peroxynitrates. In addition, we studied the CF2(OH)CF2OO, CF2(OH)CF2O, CF3CF2OO and CF3CF2O radicals, formed by the rupture of Osingle bondN and Osingle bondO bonds of the above peroxynitrates. The geometric structures of the most stable conformations were determined by density functional theory calculations. At the B3LYP/6-311++G(3df,3pd) level of theory, both peroxynitrates present dihedral angle COON values of about 104°. At the best levels of theory employed, G3(MP2)B3 and G4(MP2), the standard enthalpies of formation at 298 K derived from isodesmic reactions, are −265.6, −248.6 and −248.5 kcal mol−1 for CF2(OH)CF2OONO2, CF2(OH)CF2OO and CF2(OH)CF2O respectively; while for CF3CF2OONO2, CF3CF2OO and CF3CF2O the values of −268.2, −252.6 and −251.9 kcal mol−1 were obtained. Bond dissociation enthalpies of 25.1 and 35.0 kcal mol−1 have been predicted for the first time for CF2(OH)CF2OOsingle bondNO2 and CF2(OH)CF2Osingle bondONO2 and of 23.7 and 34.2 kcal mol−1 have been estimated for CF3CF2OOsingle bondNO2 and CF3CF2Osingle bondONO2. The obtained result of the dissociation enthalpy of CF3CF2OOsingle bondNO2 is in excellent agreement with the available experimental determination. Therefore, the Osingle bondN bond fission is the primary thermal dissociation pathway for both studied peroxynitrates.
publishDate 2015
dc.date.none.fl_str_mv 2015-04
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/11336/5082
Delvalle Mongelós, Rosa Isabel; Badenes, Maria Paula; Quantum chemical characterization of the CF2(OH)CF2OONO2 and CF3CF2OONO2 peroxynitrates and related radicals; Elsevier; Computational and Theoretical Chemistry; 1062; 4-2015; 65-73
2210-271X
url http://hdl.handle.net/11336/5082
identifier_str_mv Delvalle Mongelós, Rosa Isabel; Badenes, Maria Paula; Quantum chemical characterization of the CF2(OH)CF2OONO2 and CF3CF2OONO2 peroxynitrates and related radicals; Elsevier; Computational and Theoretical Chemistry; 1062; 4-2015; 65-73
2210-271X
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S2210271X15001395
info:eu-repo/semantics/altIdentifier/doi/
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.comptc.2015.03.024
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
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
_version_ 1842270069871083520
score 13.13397

Publicaciones similares