Vibrational dynamics of the FCH4(-) complex

Autores
Wodraszka, Robert; Palma, Juliana Isabel; Manthe, Uwe
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Motivated by recent photodetachment experiments studying resonance structures in the transition-state region of the F + CH4 → HF + CH3 reaction, the vibrational dynamics of the precursor complex CH4•F- is investigated. Delocalized vibrational eigenstates of CH4•F- are computed in full dimensionality employing the multiconfigurational time-dependent Hartree (MCTDH) approach and a recently developed iterative diagonalization approach for general multiwell systems. Different types of stereographic coordinates are used, and a corresponding general N-body kinetic energy operator is given. The calculated tunneling splittings of the ground and the lower vibrational excited states of the CH4•F- complex do not significantly exceed 1 cm-1. Comparing the converged MCTDH results for localized vibrational excitations with existing results obtained by normal-mode-based (truncated) vibrational configuration interaction calculations, significantly lower frequencies are found for excitations in the intermolecular modes.
Fil: Wodraszka, Robert. Universitat Bielefeld; Alemania
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
MCTDH
Multidymensional quantum dynamics
Vibrational spectrum
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:11336/189007
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/189007
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Vibrational dynamics of the FCH4(-) complexWodraszka, RobertPalma, Juliana IsabelManthe, UweMCTDHMultidymensional quantum dynamicsVibrational spectrumhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Motivated by recent photodetachment experiments studying resonance structures in the transition-state region of the F + CH4 → HF + CH3 reaction, the vibrational dynamics of the precursor complex CH4•F- is investigated. Delocalized vibrational eigenstates of CH4•F- are computed in full dimensionality employing the multiconfigurational time-dependent Hartree (MCTDH) approach and a recently developed iterative diagonalization approach for general multiwell systems. Different types of stereographic coordinates are used, and a corresponding general N-body kinetic energy operator is given. The calculated tunneling splittings of the ground and the lower vibrational excited states of the CH4•F- complex do not significantly exceed 1 cm-1. Comparing the converged MCTDH results for localized vibrational excitations with existing results obtained by normal-mode-based (truncated) vibrational configuration interaction calculations, significantly lower frequencies are found for excitations in the intermolecular modes.Fil: Wodraszka, Robert. Universitat Bielefeld; AlemaniaFil: 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 Chemical Society2012-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/189007Wodraszka, Robert; Palma, Juliana Isabel; Manthe, Uwe; Vibrational dynamics of the FCH4(-) complex; American Chemical Society; Journal of Physical Chemistry A; 116; 46; 6-2012; 11249-112591089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp3052642info:eu-repo/semantics/altIdentifier/doi/10.1021/jp3052642info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:13:06Zoai:ri.conicet.gov.ar:11336/189007instacron: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 10:13:06.326CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Vibrational dynamics of the FCH4(-) complex
title Vibrational dynamics of the FCH4(-) complex
spellingShingle Vibrational dynamics of the FCH4(-) complex
Wodraszka, Robert
MCTDH
Multidymensional quantum dynamics
Vibrational spectrum
title_short Vibrational dynamics of the FCH4(-) complex
title_full Vibrational dynamics of the FCH4(-) complex
title_fullStr Vibrational dynamics of the FCH4(-) complex
title_full_unstemmed Vibrational dynamics of the FCH4(-) complex
title_sort Vibrational dynamics of the FCH4(-) complex
dc.creator.none.fl_str_mv Wodraszka, Robert
Palma, Juliana Isabel
Manthe, Uwe
author Wodraszka, Robert
author_facet Wodraszka, Robert
Palma, Juliana Isabel
Manthe, Uwe
author_role author
author2 Palma, Juliana Isabel
Manthe, Uwe
author2_role author
author
dc.subject.none.fl_str_mv MCTDH
Multidymensional quantum dynamics
Vibrational spectrum
topic MCTDH
Multidymensional quantum dynamics
Vibrational spectrum
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Motivated by recent photodetachment experiments studying resonance structures in the transition-state region of the F + CH4 → HF + CH3 reaction, the vibrational dynamics of the precursor complex CH4•F- is investigated. Delocalized vibrational eigenstates of CH4•F- are computed in full dimensionality employing the multiconfigurational time-dependent Hartree (MCTDH) approach and a recently developed iterative diagonalization approach for general multiwell systems. Different types of stereographic coordinates are used, and a corresponding general N-body kinetic energy operator is given. The calculated tunneling splittings of the ground and the lower vibrational excited states of the CH4•F- complex do not significantly exceed 1 cm-1. Comparing the converged MCTDH results for localized vibrational excitations with existing results obtained by normal-mode-based (truncated) vibrational configuration interaction calculations, significantly lower frequencies are found for excitations in the intermolecular modes.
Fil: Wodraszka, Robert. Universitat Bielefeld; Alemania
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 Motivated by recent photodetachment experiments studying resonance structures in the transition-state region of the F + CH4 → HF + CH3 reaction, the vibrational dynamics of the precursor complex CH4•F- is investigated. Delocalized vibrational eigenstates of CH4•F- are computed in full dimensionality employing the multiconfigurational time-dependent Hartree (MCTDH) approach and a recently developed iterative diagonalization approach for general multiwell systems. Different types of stereographic coordinates are used, and a corresponding general N-body kinetic energy operator is given. The calculated tunneling splittings of the ground and the lower vibrational excited states of the CH4•F- complex do not significantly exceed 1 cm-1. Comparing the converged MCTDH results for localized vibrational excitations with existing results obtained by normal-mode-based (truncated) vibrational configuration interaction calculations, significantly lower frequencies are found for excitations in the intermolecular modes.
publishDate 2012
dc.date.none.fl_str_mv 2012-06
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/11336/189007
Wodraszka, Robert; Palma, Juliana Isabel; Manthe, Uwe; Vibrational dynamics of the FCH4(-) complex; American Chemical Society; Journal of Physical Chemistry A; 116; 46; 6-2012; 11249-11259
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/189007
identifier_str_mv Wodraszka, Robert; Palma, Juliana Isabel; Manthe, Uwe; Vibrational dynamics of the FCH4(-) complex; American Chemical Society; Journal of Physical Chemistry A; 116; 46; 6-2012; 11249-11259
1089-5639
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp3052642
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp3052642
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_ 1844614044609150976
score 13.070432

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