Non-adiabatic effects in F + CHD3 reactive scattering

Autores
Palma, Juliana Isabel; Manthe, Uwe
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The effect of non-adiabatic transitions on the F(2P) + CHD3(ν1) → DF + CHD2 and F(2P) + CHD3(ν1) → HF + CD3 reactions is investigated. The dynamics of the nuclei was simulated using trajectory surface hopping and a vibronically and spin-orbit coupled diabatic potential energy matrix. To facilitate the calculations, the fewest switching algorithm of Tully was adapted to the use of a complex diabatic potential energy matrix. For reactions of CHD3 with ground state fluorine atoms, F(2P3/2), the ratio between the previously computed adiabatic cross sections and the non-adiabatic ones was found to range from 1.4 to 2.1. The actual ratio depends on the translational energy and the initial vibrational state of CHD3. The total reactivity of CHD3(ν1 = 1) was found to be always larger than that of CHD3(ν1=0) mainly because of the increase in the cross sections for the HF + CD3 channel. Thus, the inclusion of non-adiabatic transitions in the theoretical treatment cannot resolve the existing disagreement between theory and experiment. Cross sections for the reaction of CHD3 with spin-orbit excited fluorine atoms, F(2P1/2), were found to be significantly smaller than the ones for reaction with F(2P3/2).
Fil: Palma, Juliana Isabel. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Manthe, Uwe. Universitat Bielefeld; Alemania
Materia
Reaction dynamics
Non-adiabatic effects
F+CH4
F+CHD3
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:11336/72613

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network_name_str CONICET Digital (CONICET)
spelling Non-adiabatic effects in F + CHD3 reactive scatteringPalma, Juliana IsabelManthe, UweReaction dynamicsNon-adiabatic effectsF+CH4F+CHD3https://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The effect of non-adiabatic transitions on the F(2P) + CHD3(ν1) → DF + CHD2 and F(2P) + CHD3(ν1) → HF + CD3 reactions is investigated. The dynamics of the nuclei was simulated using trajectory surface hopping and a vibronically and spin-orbit coupled diabatic potential energy matrix. To facilitate the calculations, the fewest switching algorithm of Tully was adapted to the use of a complex diabatic potential energy matrix. For reactions of CHD3 with ground state fluorine atoms, F(2P3/2), the ratio between the previously computed adiabatic cross sections and the non-adiabatic ones was found to range from 1.4 to 2.1. The actual ratio depends on the translational energy and the initial vibrational state of CHD3. The total reactivity of CHD3(ν1 = 1) was found to be always larger than that of CHD3(ν1=0) mainly because of the increase in the cross sections for the HF + CD3 channel. Thus, the inclusion of non-adiabatic transitions in the theoretical treatment cannot resolve the existing disagreement between theory and experiment. Cross sections for the reaction of CHD3 with spin-orbit excited fluorine atoms, F(2P1/2), were found to be significantly smaller than the ones for reaction with F(2P3/2).Fil: Palma, Juliana Isabel. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Manthe, Uwe. Universitat Bielefeld; AlemaniaAmerican Institute of Physics2017-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/72613Palma, Juliana Isabel; Manthe, Uwe; Non-adiabatic effects in F + CHD3 reactive scattering; American Institute of Physics; Journal of Chemical Physics; 146; 21; 6-2017; 1-9; 2141170021-9606CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1063/1.4984593info:eu-repo/semantics/altIdentifier/url/https://aip.scitation.org/doi/10.1063/1.4984593info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T15:01:24Zoai:ri.conicet.gov.ar:11336/72613instacron: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:34982025-10-15 15:01:24.485CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Non-adiabatic effects in F + CHD3 reactive scattering
title Non-adiabatic effects in F + CHD3 reactive scattering
spellingShingle Non-adiabatic effects in F + CHD3 reactive scattering
Palma, Juliana Isabel
Reaction dynamics
Non-adiabatic effects
F+CH4
F+CHD3
title_short Non-adiabatic effects in F + CHD3 reactive scattering
title_full Non-adiabatic effects in F + CHD3 reactive scattering
title_fullStr Non-adiabatic effects in F + CHD3 reactive scattering
title_full_unstemmed Non-adiabatic effects in F + CHD3 reactive scattering
title_sort Non-adiabatic effects in F + CHD3 reactive scattering
dc.creator.none.fl_str_mv Palma, Juliana Isabel
Manthe, Uwe
author Palma, Juliana Isabel
author_facet Palma, Juliana Isabel
Manthe, Uwe
author_role author
author2 Manthe, Uwe
author2_role author
dc.subject.none.fl_str_mv Reaction dynamics
Non-adiabatic effects
F+CH4
F+CHD3
topic Reaction dynamics
Non-adiabatic effects
F+CH4
F+CHD3
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 effect of non-adiabatic transitions on the F(2P) + CHD3(ν1) → DF + CHD2 and F(2P) + CHD3(ν1) → HF + CD3 reactions is investigated. The dynamics of the nuclei was simulated using trajectory surface hopping and a vibronically and spin-orbit coupled diabatic potential energy matrix. To facilitate the calculations, the fewest switching algorithm of Tully was adapted to the use of a complex diabatic potential energy matrix. For reactions of CHD3 with ground state fluorine atoms, F(2P3/2), the ratio between the previously computed adiabatic cross sections and the non-adiabatic ones was found to range from 1.4 to 2.1. The actual ratio depends on the translational energy and the initial vibrational state of CHD3. The total reactivity of CHD3(ν1 = 1) was found to be always larger than that of CHD3(ν1=0) mainly because of the increase in the cross sections for the HF + CD3 channel. Thus, the inclusion of non-adiabatic transitions in the theoretical treatment cannot resolve the existing disagreement between theory and experiment. Cross sections for the reaction of CHD3 with spin-orbit excited fluorine atoms, F(2P1/2), were found to be significantly smaller than the ones for reaction with F(2P3/2).
Fil: Palma, Juliana Isabel. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Manthe, Uwe. Universitat Bielefeld; Alemania
description The effect of non-adiabatic transitions on the F(2P) + CHD3(ν1) → DF + CHD2 and F(2P) + CHD3(ν1) → HF + CD3 reactions is investigated. The dynamics of the nuclei was simulated using trajectory surface hopping and a vibronically and spin-orbit coupled diabatic potential energy matrix. To facilitate the calculations, the fewest switching algorithm of Tully was adapted to the use of a complex diabatic potential energy matrix. For reactions of CHD3 with ground state fluorine atoms, F(2P3/2), the ratio between the previously computed adiabatic cross sections and the non-adiabatic ones was found to range from 1.4 to 2.1. The actual ratio depends on the translational energy and the initial vibrational state of CHD3. The total reactivity of CHD3(ν1 = 1) was found to be always larger than that of CHD3(ν1=0) mainly because of the increase in the cross sections for the HF + CD3 channel. Thus, the inclusion of non-adiabatic transitions in the theoretical treatment cannot resolve the existing disagreement between theory and experiment. Cross sections for the reaction of CHD3 with spin-orbit excited fluorine atoms, F(2P1/2), were found to be significantly smaller than the ones for reaction with F(2P3/2).
publishDate 2017
dc.date.none.fl_str_mv 2017-06
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/11336/72613
Palma, Juliana Isabel; Manthe, Uwe; Non-adiabatic effects in F + CHD3 reactive scattering; American Institute of Physics; Journal of Chemical Physics; 146; 21; 6-2017; 1-9; 214117
0021-9606
CONICET Digital
CONICET
url http://hdl.handle.net/11336/72613
identifier_str_mv Palma, Juliana Isabel; Manthe, Uwe; Non-adiabatic effects in F + CHD3 reactive scattering; American Institute of Physics; Journal of Chemical Physics; 146; 21; 6-2017; 1-9; 214117
0021-9606
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1063/1.4984593
info:eu-repo/semantics/altIdentifier/url/https://aip.scitation.org/doi/10.1063/1.4984593
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 Institute of Physics
publisher.none.fl_str_mv American Institute of Physics
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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