Infrared spectroscopy of OH··CH3OH: Hydrogen-bonded intermediate along the hydrogen abstraction reaction path

Autores
Hernández, Federico Javier; Brice, Joseph; Leavitt, Christopher M.; Pino, Gustavo Ariel; Douberly, Gary E.
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Substantial non-Arrhenius behavior has been previously observed in the low temperature reaction between the hydroxyl radical and methanol. This behavior can be rationalized assuming the stabilization of an association adduct in the entrance channel of the reaction, from which barrier penetration via quantum mechanical tunneling produces the CH3O radical and H2O. Helium nanodroplet isolation and a serial pick-up technique are used to stabilize the hydrogen bonded prereactive OH··CH3OH complex. Mass spectrometry and infrared spectroscopy are used to confirm its production and probe the OH stretch vibrations. Stark spectroscopy reveals the magnitude of the permanent electric dipole moment, which is compared to ab initio calculations that account for wide-amplitude motion in the complex. The vibrationally averaged structure has Cs symmetry with the OH moiety hydrogen bonded to the hydroxyl group of methanol. Nevertheless, the zero-point level of the complex exhibits a wave function significantly delocalized over a bending coordinate leading to the transition state of the CH3O producing reaction.
Fil: Hernández, Federico Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Brice, Joseph. University of Georgia; Estados Unidos
Fil: Leavitt, Christopher M.. University of Georgia; Estados Unidos
Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Douberly, Gary E.. University of Georgia; Estados Unidos
Materia
Espectroscopia Laser
Agregados Moleculares
Espectroscopia Infrarroja
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:11336/47174
Acceder
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network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Infrared spectroscopy of OH··CH3OH: Hydrogen-bonded intermediate along the hydrogen abstraction reaction pathHernández, Federico JavierBrice, JosephLeavitt, Christopher M.Pino, Gustavo ArielDouberly, Gary E.Espectroscopia LaserAgregados MolecularesEspectroscopia Infrarrojahttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1Substantial non-Arrhenius behavior has been previously observed in the low temperature reaction between the hydroxyl radical and methanol. This behavior can be rationalized assuming the stabilization of an association adduct in the entrance channel of the reaction, from which barrier penetration via quantum mechanical tunneling produces the CH3O radical and H2O. Helium nanodroplet isolation and a serial pick-up technique are used to stabilize the hydrogen bonded prereactive OH··CH3OH complex. Mass spectrometry and infrared spectroscopy are used to confirm its production and probe the OH stretch vibrations. Stark spectroscopy reveals the magnitude of the permanent electric dipole moment, which is compared to ab initio calculations that account for wide-amplitude motion in the complex. The vibrationally averaged structure has Cs symmetry with the OH moiety hydrogen bonded to the hydroxyl group of methanol. Nevertheless, the zero-point level of the complex exhibits a wave function significantly delocalized over a bending coordinate leading to the transition state of the CH3O producing reaction.Fil: Hernández, Federico Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Brice, Joseph. University of Georgia; Estados UnidosFil: Leavitt, Christopher M.. University of Georgia; Estados UnidosFil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Douberly, Gary E.. University of Georgia; Estados UnidosAmerican Chemical Society2015-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/47174Hernández, Federico Javier; Brice, Joseph; Leavitt, Christopher M.; Pino, Gustavo Ariel; Douberly, Gary E.; Infrared spectroscopy of OH··CH3OH: Hydrogen-bonded intermediate along the hydrogen abstraction reaction path; American Chemical Society; Journal of Physical Chemistry A; 119; 29; 7-2015; 8125-81321089-56391520-5215CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpca.5b04875info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.5b04875info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T12:18:50Zoai:ri.conicet.gov.ar:11336/47174instacron: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 12:18:50.532CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Infrared spectroscopy of OH··CH3OH: Hydrogen-bonded intermediate along the hydrogen abstraction reaction path
title Infrared spectroscopy of OH··CH3OH: Hydrogen-bonded intermediate along the hydrogen abstraction reaction path
spellingShingle Infrared spectroscopy of OH··CH3OH: Hydrogen-bonded intermediate along the hydrogen abstraction reaction path
Hernández, Federico Javier
Espectroscopia Laser
Agregados Moleculares
Espectroscopia Infrarroja
title_short Infrared spectroscopy of OH··CH3OH: Hydrogen-bonded intermediate along the hydrogen abstraction reaction path
title_full Infrared spectroscopy of OH··CH3OH: Hydrogen-bonded intermediate along the hydrogen abstraction reaction path
title_fullStr Infrared spectroscopy of OH··CH3OH: Hydrogen-bonded intermediate along the hydrogen abstraction reaction path
title_full_unstemmed Infrared spectroscopy of OH··CH3OH: Hydrogen-bonded intermediate along the hydrogen abstraction reaction path
title_sort Infrared spectroscopy of OH··CH3OH: Hydrogen-bonded intermediate along the hydrogen abstraction reaction path
dc.creator.none.fl_str_mv Hernández, Federico Javier
Brice, Joseph
Leavitt, Christopher M.
Pino, Gustavo Ariel
Douberly, Gary E.
author Hernández, Federico Javier
author_facet Hernández, Federico Javier
Brice, Joseph
Leavitt, Christopher M.
Pino, Gustavo Ariel
Douberly, Gary E.
author_role author
author2 Brice, Joseph
Leavitt, Christopher M.
Pino, Gustavo Ariel
Douberly, Gary E.
author2_role author
author
author
author
dc.subject.none.fl_str_mv Espectroscopia Laser
Agregados Moleculares
Espectroscopia Infrarroja
topic Espectroscopia Laser
Agregados Moleculares
Espectroscopia Infrarroja
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Substantial non-Arrhenius behavior has been previously observed in the low temperature reaction between the hydroxyl radical and methanol. This behavior can be rationalized assuming the stabilization of an association adduct in the entrance channel of the reaction, from which barrier penetration via quantum mechanical tunneling produces the CH3O radical and H2O. Helium nanodroplet isolation and a serial pick-up technique are used to stabilize the hydrogen bonded prereactive OH··CH3OH complex. Mass spectrometry and infrared spectroscopy are used to confirm its production and probe the OH stretch vibrations. Stark spectroscopy reveals the magnitude of the permanent electric dipole moment, which is compared to ab initio calculations that account for wide-amplitude motion in the complex. The vibrationally averaged structure has Cs symmetry with the OH moiety hydrogen bonded to the hydroxyl group of methanol. Nevertheless, the zero-point level of the complex exhibits a wave function significantly delocalized over a bending coordinate leading to the transition state of the CH3O producing reaction.
Fil: Hernández, Federico Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Brice, Joseph. University of Georgia; Estados Unidos
Fil: Leavitt, Christopher M.. University of Georgia; Estados Unidos
Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Douberly, Gary E.. University of Georgia; Estados Unidos
description Substantial non-Arrhenius behavior has been previously observed in the low temperature reaction between the hydroxyl radical and methanol. This behavior can be rationalized assuming the stabilization of an association adduct in the entrance channel of the reaction, from which barrier penetration via quantum mechanical tunneling produces the CH3O radical and H2O. Helium nanodroplet isolation and a serial pick-up technique are used to stabilize the hydrogen bonded prereactive OH··CH3OH complex. Mass spectrometry and infrared spectroscopy are used to confirm its production and probe the OH stretch vibrations. Stark spectroscopy reveals the magnitude of the permanent electric dipole moment, which is compared to ab initio calculations that account for wide-amplitude motion in the complex. The vibrationally averaged structure has Cs symmetry with the OH moiety hydrogen bonded to the hydroxyl group of methanol. Nevertheless, the zero-point level of the complex exhibits a wave function significantly delocalized over a bending coordinate leading to the transition state of the CH3O producing reaction.
publishDate 2015
dc.date.none.fl_str_mv 2015-07
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/11336/47174
Hernández, Federico Javier; Brice, Joseph; Leavitt, Christopher M.; Pino, Gustavo Ariel; Douberly, Gary E.; Infrared spectroscopy of OH··CH3OH: Hydrogen-bonded intermediate along the hydrogen abstraction reaction path; American Chemical Society; Journal of Physical Chemistry A; 119; 29; 7-2015; 8125-8132
1089-5639
1520-5215
CONICET Digital
CONICET
url http://hdl.handle.net/11336/47174
identifier_str_mv Hernández, Federico Javier; Brice, Joseph; Leavitt, Christopher M.; Pino, Gustavo Ariel; Douberly, Gary E.; Infrared spectroscopy of OH··CH3OH: Hydrogen-bonded intermediate along the hydrogen abstraction reaction path; American Chemical Society; Journal of Physical Chemistry A; 119; 29; 7-2015; 8125-8132
1089-5639
1520-5215
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://pubs.acs.org/doi/10.1021/acs.jpca.5b04875
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.5b04875
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
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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_ 1846782622562254848
score 12.982451

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