Quantum chemical and kinetic study of the CCl 2 self-recombination reaction

Autores
Gómez, Nicolás Damián; Codnia, Jorge; Azcárate, María Laura; Cobos, Carlos Jorge
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The temperature and pressure dependencies of the rate constant of the recombination reaction CCl2 + CCl2 + M → C2Cl4 + M have been theoretically studied between 300 and 2000 K. Quantum-chemical calculations were employed to characterize relevant parts of the potential energy surface of this process. The limiting rate constants were analyzed using the unimolecular reaction theory. The resulting low pressure rate constant can be represented as k0 = [Ar] 3.5 × 10−23 (T/300 K)−8.7 exp(−1560 K/T) cm3 molecule−1 s−1. The high pressure rate constants derived from a simplified statistical adiabatic channel model (SSACM) and from a SACM combined with classical trajectory calculations (SACM/CT) are k∞ = (1.7 ± 1.0) × 10−12 (T/300)0.8 ± 0.1 cm3 molecule−1 s−1 and k∞ = (5.4 ± 3.0) × 10−13 (T/300)0.7 ± 0.1 cm3 molecule−1 s−1. The falloff curves were represented in terms of these limiting rate constants. Reported experimental results are satisfactorily described with the present model. The calculations indicate that the CCl2 + CCl2 reaction proceeds via the stabilization of C2Cl4, with a contribution of the C2Cl3 + Cl → C2Cl4 reaction, and at sufficiently high temperatures the channel CCl2 + CCl2 → C2Cl2 + 2Cl becomes relevant.
Fil: Gómez, Nicolás Damián. Consejo Nacional de Investigaciones Científicas y Técnicas. Unidad de Investigación y Desarrollo Estratégico para la Defensa. Ministerio de Defensa. Unidad de Investigación y Desarrollo Estratégico para la Defensa; Argentina
Fil: Codnia, Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Unidad de Investigación y Desarrollo Estratégico para la Defensa. Ministerio de Defensa. Unidad de Investigación y Desarrollo Estratégico para la Defensa; Argentina
Fil: Azcárate, María Laura. Consejo Nacional de Investigaciones Científicas y Técnicas. Unidad de Investigación y Desarrollo Estratégico para la Defensa. Ministerio de Defensa. Unidad de Investigación y Desarrollo Estratégico para la Defensa; Argentina
Fil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Materia
Ccl2
C2cl4
Quantum-Chemical Calculations
Statistical Adiabatic Channel Model/Classical Trajectory Calculations
Recombination Reactions
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:11336/41412
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/41412
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Quantum chemical and kinetic study of the CCl 2 self-recombination reactionGómez, Nicolás DamiánCodnia, JorgeAzcárate, María LauraCobos, Carlos JorgeCcl2C2cl4Quantum-Chemical CalculationsStatistical Adiabatic Channel Model/Classical Trajectory CalculationsRecombination Reactionshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The temperature and pressure dependencies of the rate constant of the recombination reaction CCl2 + CCl2 + M → C2Cl4 + M have been theoretically studied between 300 and 2000 K. Quantum-chemical calculations were employed to characterize relevant parts of the potential energy surface of this process. The limiting rate constants were analyzed using the unimolecular reaction theory. The resulting low pressure rate constant can be represented as k0 = [Ar] 3.5 × 10−23 (T/300 K)−8.7 exp(−1560 K/T) cm3 molecule−1 s−1. The high pressure rate constants derived from a simplified statistical adiabatic channel model (SSACM) and from a SACM combined with classical trajectory calculations (SACM/CT) are k∞ = (1.7 ± 1.0) × 10−12 (T/300)0.8 ± 0.1 cm3 molecule−1 s−1 and k∞ = (5.4 ± 3.0) × 10−13 (T/300)0.7 ± 0.1 cm3 molecule−1 s−1. The falloff curves were represented in terms of these limiting rate constants. Reported experimental results are satisfactorily described with the present model. The calculations indicate that the CCl2 + CCl2 reaction proceeds via the stabilization of C2Cl4, with a contribution of the C2Cl3 + Cl → C2Cl4 reaction, and at sufficiently high temperatures the channel CCl2 + CCl2 → C2Cl2 + 2Cl becomes relevant.Fil: Gómez, Nicolás Damián. Consejo Nacional de Investigaciones Científicas y Técnicas. Unidad de Investigación y Desarrollo Estratégico para la Defensa. Ministerio de Defensa. Unidad de Investigación y Desarrollo Estratégico para la Defensa; ArgentinaFil: Codnia, Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Unidad de Investigación y Desarrollo Estratégico para la Defensa. Ministerio de Defensa. Unidad de Investigación y Desarrollo Estratégico para la Defensa; ArgentinaFil: Azcárate, María Laura. Consejo Nacional de Investigaciones Científicas y Técnicas. Unidad de Investigación y Desarrollo Estratégico para la Defensa. Ministerio de Defensa. Unidad de Investigación y Desarrollo Estratégico para la Defensa; ArgentinaFil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaElsevier2017-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/41412Gómez, Nicolás Damián; Codnia, Jorge; Azcárate, María Laura; Cobos, Carlos Jorge; Quantum chemical and kinetic study of the CCl 2 self-recombination reaction; Elsevier; Computational and Theoretical Chemistry; 1121; 12-2017; 1-102210-271XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.comptc.2017.10.004info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S2210271X17304425info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:34:46Zoai:ri.conicet.gov.ar:11336/41412instacron: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:34982025-09-29 09:34:47.251CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Quantum chemical and kinetic study of the CCl 2 self-recombination reaction
title Quantum chemical and kinetic study of the CCl 2 self-recombination reaction
spellingShingle Quantum chemical and kinetic study of the CCl 2 self-recombination reaction
Gómez, Nicolás Damián
Ccl2
C2cl4
Quantum-Chemical Calculations
Statistical Adiabatic Channel Model/Classical Trajectory Calculations
Recombination Reactions
title_short Quantum chemical and kinetic study of the CCl 2 self-recombination reaction
title_full Quantum chemical and kinetic study of the CCl 2 self-recombination reaction
title_fullStr Quantum chemical and kinetic study of the CCl 2 self-recombination reaction
title_full_unstemmed Quantum chemical and kinetic study of the CCl 2 self-recombination reaction
title_sort Quantum chemical and kinetic study of the CCl 2 self-recombination reaction
dc.creator.none.fl_str_mv Gómez, Nicolás Damián
Codnia, Jorge
Azcárate, María Laura
Cobos, Carlos Jorge
author Gómez, Nicolás Damián
author_facet Gómez, Nicolás Damián
Codnia, Jorge
Azcárate, María Laura
Cobos, Carlos Jorge
author_role author
author2 Codnia, Jorge
Azcárate, María Laura
Cobos, Carlos Jorge
author2_role author
author
author
dc.subject.none.fl_str_mv Ccl2
C2cl4
Quantum-Chemical Calculations
Statistical Adiabatic Channel Model/Classical Trajectory Calculations
Recombination Reactions
topic Ccl2
C2cl4
Quantum-Chemical Calculations
Statistical Adiabatic Channel Model/Classical Trajectory Calculations
Recombination Reactions
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 temperature and pressure dependencies of the rate constant of the recombination reaction CCl2 + CCl2 + M → C2Cl4 + M have been theoretically studied between 300 and 2000 K. Quantum-chemical calculations were employed to characterize relevant parts of the potential energy surface of this process. The limiting rate constants were analyzed using the unimolecular reaction theory. The resulting low pressure rate constant can be represented as k0 = [Ar] 3.5 × 10−23 (T/300 K)−8.7 exp(−1560 K/T) cm3 molecule−1 s−1. The high pressure rate constants derived from a simplified statistical adiabatic channel model (SSACM) and from a SACM combined with classical trajectory calculations (SACM/CT) are k∞ = (1.7 ± 1.0) × 10−12 (T/300)0.8 ± 0.1 cm3 molecule−1 s−1 and k∞ = (5.4 ± 3.0) × 10−13 (T/300)0.7 ± 0.1 cm3 molecule−1 s−1. The falloff curves were represented in terms of these limiting rate constants. Reported experimental results are satisfactorily described with the present model. The calculations indicate that the CCl2 + CCl2 reaction proceeds via the stabilization of C2Cl4, with a contribution of the C2Cl3 + Cl → C2Cl4 reaction, and at sufficiently high temperatures the channel CCl2 + CCl2 → C2Cl2 + 2Cl becomes relevant.
Fil: Gómez, Nicolás Damián. Consejo Nacional de Investigaciones Científicas y Técnicas. Unidad de Investigación y Desarrollo Estratégico para la Defensa. Ministerio de Defensa. Unidad de Investigación y Desarrollo Estratégico para la Defensa; Argentina
Fil: Codnia, Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Unidad de Investigación y Desarrollo Estratégico para la Defensa. Ministerio de Defensa. Unidad de Investigación y Desarrollo Estratégico para la Defensa; Argentina
Fil: Azcárate, María Laura. Consejo Nacional de Investigaciones Científicas y Técnicas. Unidad de Investigación y Desarrollo Estratégico para la Defensa. Ministerio de Defensa. Unidad de Investigación y Desarrollo Estratégico para la Defensa; Argentina
Fil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
description The temperature and pressure dependencies of the rate constant of the recombination reaction CCl2 + CCl2 + M → C2Cl4 + M have been theoretically studied between 300 and 2000 K. Quantum-chemical calculations were employed to characterize relevant parts of the potential energy surface of this process. The limiting rate constants were analyzed using the unimolecular reaction theory. The resulting low pressure rate constant can be represented as k0 = [Ar] 3.5 × 10−23 (T/300 K)−8.7 exp(−1560 K/T) cm3 molecule−1 s−1. The high pressure rate constants derived from a simplified statistical adiabatic channel model (SSACM) and from a SACM combined with classical trajectory calculations (SACM/CT) are k∞ = (1.7 ± 1.0) × 10−12 (T/300)0.8 ± 0.1 cm3 molecule−1 s−1 and k∞ = (5.4 ± 3.0) × 10−13 (T/300)0.7 ± 0.1 cm3 molecule−1 s−1. The falloff curves were represented in terms of these limiting rate constants. Reported experimental results are satisfactorily described with the present model. The calculations indicate that the CCl2 + CCl2 reaction proceeds via the stabilization of C2Cl4, with a contribution of the C2Cl3 + Cl → C2Cl4 reaction, and at sufficiently high temperatures the channel CCl2 + CCl2 → C2Cl2 + 2Cl becomes relevant.
publishDate 2017
dc.date.none.fl_str_mv 2017-12
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/11336/41412
Gómez, Nicolás Damián; Codnia, Jorge; Azcárate, María Laura; Cobos, Carlos Jorge; Quantum chemical and kinetic study of the CCl 2 self-recombination reaction; Elsevier; Computational and Theoretical Chemistry; 1121; 12-2017; 1-10
2210-271X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/41412
identifier_str_mv Gómez, Nicolás Damián; Codnia, Jorge; Azcárate, María Laura; Cobos, Carlos Jorge; Quantum chemical and kinetic study of the CCl 2 self-recombination reaction; Elsevier; Computational and Theoretical Chemistry; 1121; 12-2017; 1-10
2210-271X
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.comptc.2017.10.004
info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S2210271X17304425
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
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score 13.070432

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