Effect of temperature on the gas-phase reaction of CH3CN with OH radicals: experimental (T = 11.7–177.5 K) and computational (T = 10–400 K) kinetic study†

Acetonitrile (CH3CN) is present in the interstellar medium (ISM) in a variety of environments. However, at the ultracold temperatures of the ISM, radical-molecule reactions are not widely investigated because of the experimental handicap of getting organic molecules in the gas phase by conventional...

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Autores: González, Daniel, Canosa, André, Martínez Núñez, Emilio, Fernández Ramos, Antonio, Ballesteros, Bernabé, Agúndez, Marcelino, Cernicharo, José, Jiménez, Elena
Tipo de recurso: artículo
Fecha de publicación:2024
País:España
Institución:Universidad de Santiago de Compostela (USC)
Repositorio:Minerva. Repositorio Institucional de la Universidad de Santiago de Compostela
Idioma:inglés
OAI Identifier:oai:minerva.usc.gal:10347/38822
Acceso en línea:https://hdl.handle.net/10347/38822
Access Level:acceso abierto
Palabra clave:Acetonitrilo
Cianuro de metilo
2307 Química física
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spelling Effect of temperature on the gas-phase reaction of CH3CN with OH radicals: experimental (T = 11.7–177.5 K) and computational (T = 10–400 K) kinetic study†González, DanielCanosa, AndréMartínez Núñez, EmilioFernández Ramos, AntonioBallesteros, BernabéAgúndez, MarcelinoCernicharo, JoséJiménez, ElenaAcetonitriloCianuro de metilo2307 Química físicaAcetonitrile (CH3CN) is present in the interstellar medium (ISM) in a variety of environments. However, at the ultracold temperatures of the ISM, radical-molecule reactions are not widely investigated because of the experimental handicap of getting organic molecules in the gas phase by conventional techniques. The CRESU (French acronym for Reaction Kinetics in a Uniform Supersonic Flow) technique solves this problem. For this reason, we present in this work the kinetic study of the gas-phase reaction of CH3CN with one of the most ubiquitous radicals, the hydroxyl (OH) radical, as a function of temperature (11.7–177.5 K). The kinetic technique employed to investigate the CH3CN + OH reaction was the pulsed laser photolysis-laser induced fluorescence. The rate coefficient for this reaction k(T) has been observed to drastically increase from 177.5 K to 107.0 K (about 2 orders of magnitude), while the increase in k(T) from 107.0 K to 11.7 K was milder (around 4 times). The temperature dependent expressions for k(T) are provided in the two distinct T-ranges, excluding the upper limit obtained for k(177.5 K): Image ID:d3cp04944b-t1.gifIn addition, the rate coefficients estimated by the canonical competitive unified statistical (CCUS) theory show a similar behaviour to the experimental results, when evaluated within the high-pressure limit. This is consistent with the experimentally observed independence of k(T) with total gas density at selected temperatures. Astrochemical networks, such as the KIDA database or UMIST, do not include the CH3CN + OH reaction as a potential depletion process for acetonitrile in the ISM because the current studies predict very low rate coefficients at IS temperatures. According to the model (T = 10 K), the impact of the titled reaction on the abundances of CH3CN appears to be negligible in dark molecular clouds of the ISM (∼1% of the total depletion reactions included in UMIST network). With respect to the potential formation of the CH2CN radical in those environments, even in the most favourable scenario, where this radical could be formed in a 100% yield from the CH3CN + OH reaction, this route would only contribute around 2% to the current assumed formation routes by the UMIST network.Royal Society of ChemistryUniversidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)Universidade de Santiago de Compostela. Departamento de Química Física20242024-01-0120242024-01-01journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/10347/38822reponame:Minerva. Repositorio Institucional de la Universidad de Santiago de Compostelainstname:Universidad de Santiago de Compostela (USC)Inglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:minerva.usc.gal:10347/388222026-06-15T12:47:27Z
dc.title.none.fl_str_mv Effect of temperature on the gas-phase reaction of CH3CN with OH radicals: experimental (T = 11.7–177.5 K) and computational (T = 10–400 K) kinetic study†
title Effect of temperature on the gas-phase reaction of CH3CN with OH radicals: experimental (T = 11.7–177.5 K) and computational (T = 10–400 K) kinetic study†
spellingShingle Effect of temperature on the gas-phase reaction of CH3CN with OH radicals: experimental (T = 11.7–177.5 K) and computational (T = 10–400 K) kinetic study†
González, Daniel
Acetonitrilo
Cianuro de metilo
2307 Química física
title_short Effect of temperature on the gas-phase reaction of CH3CN with OH radicals: experimental (T = 11.7–177.5 K) and computational (T = 10–400 K) kinetic study†
title_full Effect of temperature on the gas-phase reaction of CH3CN with OH radicals: experimental (T = 11.7–177.5 K) and computational (T = 10–400 K) kinetic study†
title_fullStr Effect of temperature on the gas-phase reaction of CH3CN with OH radicals: experimental (T = 11.7–177.5 K) and computational (T = 10–400 K) kinetic study†
title_full_unstemmed Effect of temperature on the gas-phase reaction of CH3CN with OH radicals: experimental (T = 11.7–177.5 K) and computational (T = 10–400 K) kinetic study†
title_sort Effect of temperature on the gas-phase reaction of CH3CN with OH radicals: experimental (T = 11.7–177.5 K) and computational (T = 10–400 K) kinetic study†
dc.creator.none.fl_str_mv González, Daniel
Canosa, André
Martínez Núñez, Emilio
Fernández Ramos, Antonio
Ballesteros, Bernabé
Agúndez, Marcelino
Cernicharo, José
Jiménez, Elena
author González, Daniel
author_facet González, Daniel
Canosa, André
Martínez Núñez, Emilio
Fernández Ramos, Antonio
Ballesteros, Bernabé
Agúndez, Marcelino
Cernicharo, José
Jiménez, Elena
author_role author
author2 Canosa, André
Martínez Núñez, Emilio
Fernández Ramos, Antonio
Ballesteros, Bernabé
Agúndez, Marcelino
Cernicharo, José
Jiménez, Elena
author2_role author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)
Universidade de Santiago de Compostela. Departamento de Química Física
dc.subject.none.fl_str_mv Acetonitrilo
Cianuro de metilo
2307 Química física
topic Acetonitrilo
Cianuro de metilo
2307 Química física
description Acetonitrile (CH3CN) is present in the interstellar medium (ISM) in a variety of environments. However, at the ultracold temperatures of the ISM, radical-molecule reactions are not widely investigated because of the experimental handicap of getting organic molecules in the gas phase by conventional techniques. The CRESU (French acronym for Reaction Kinetics in a Uniform Supersonic Flow) technique solves this problem. For this reason, we present in this work the kinetic study of the gas-phase reaction of CH3CN with one of the most ubiquitous radicals, the hydroxyl (OH) radical, as a function of temperature (11.7–177.5 K). The kinetic technique employed to investigate the CH3CN + OH reaction was the pulsed laser photolysis-laser induced fluorescence. The rate coefficient for this reaction k(T) has been observed to drastically increase from 177.5 K to 107.0 K (about 2 orders of magnitude), while the increase in k(T) from 107.0 K to 11.7 K was milder (around 4 times). The temperature dependent expressions for k(T) are provided in the two distinct T-ranges, excluding the upper limit obtained for k(177.5 K): Image ID:d3cp04944b-t1.gifIn addition, the rate coefficients estimated by the canonical competitive unified statistical (CCUS) theory show a similar behaviour to the experimental results, when evaluated within the high-pressure limit. This is consistent with the experimentally observed independence of k(T) with total gas density at selected temperatures. Astrochemical networks, such as the KIDA database or UMIST, do not include the CH3CN + OH reaction as a potential depletion process for acetonitrile in the ISM because the current studies predict very low rate coefficients at IS temperatures. According to the model (T = 10 K), the impact of the titled reaction on the abundances of CH3CN appears to be negligible in dark molecular clouds of the ISM (∼1% of the total depletion reactions included in UMIST network). With respect to the potential formation of the CH2CN radical in those environments, even in the most favourable scenario, where this radical could be formed in a 100% yield from the CH3CN + OH reaction, this route would only contribute around 2% to the current assumed formation routes by the UMIST network.
publishDate 2024
dc.date.none.fl_str_mv 2024
2024-01-01
2024
2024-01-01
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/10347/38822
url https://hdl.handle.net/10347/38822
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv reponame:Minerva. Repositorio Institucional de la Universidad de Santiago de Compostela
instname:Universidad de Santiago de Compostela (USC)
instname_str Universidad de Santiago de Compostela (USC)
reponame_str Minerva. Repositorio Institucional de la Universidad de Santiago de Compostela
collection Minerva. Repositorio Institucional de la Universidad de Santiago de Compostela
repository.name.fl_str_mv
repository.mail.fl_str_mv
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