Coupled diabatic potential energy surfaces for studying the nonadiabatic dynamics at conical intersections in angular resolved photodetachment simulations of OHF−→OHF+e−

[EN]An energy-based method is proposed for the diabatization of the OH((2)Pi)+F(P-2)-> O(P-3)+HF((1)Sigma(+)) reaction. It is demonstrated that the diabatic representation obtained is regularized, i.e., the residual derivative couplings do not present singularities at the conical intersections ap...

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Autores: Gómez Carrasco, Susana Raquel, Aguado, Alfredo, Paniagua, Miguel, Roncero, Octavio
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2006
País:España
Institución:Universidad de Salamanca (USAL)
Repositorio:GREDOS. Repositorio Institucional de la Universidad de Salamanca
OAI Identifier:oai:gredos.usal.es:10366/169555
Acceso en línea:http://hdl.handle.net/10366/169555
Access Level:acceso abierto
Palabra clave:Transition state dynamics
Electronic states
Born Oppenheimer
Rate constant
OHF
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spelling Coupled diabatic potential energy surfaces for studying the nonadiabatic dynamics at conical intersections in angular resolved photodetachment simulations of OHF−→OHF+e−Gómez Carrasco, Susana RaquelAguado, AlfredoPaniagua, MiguelRoncero, OctavioTransition state dynamicsElectronic statesBorn OppenheimerRate constantOHF[EN]An energy-based method is proposed for the diabatization of the OH((2)Pi)+F(P-2)-> O(P-3)+HF((1)Sigma(+)) reaction. It is demonstrated that the diabatic representation obtained is regularized, i.e., the residual derivative couplings do not present singularities at the conical intersections appearing along the reaction path. This method only requires the knowledge of the 1,2 (3)A(') and 1 (3)A(') eigenvalues and does not require any adjustable parameter. Thus, many convergence problems arising in other derivative-based diabatization methods are avoided, and the description of the configuration space along the reaction path is enormously simplified. Three-dimensional coupled diabatic energy surfaces are obtained by an interpolation procedure using approximate to 4000 accurate ab initio points. The angular resolved photodetachment cross sections are obtained in the diabatic and adiabatic representations using a wave packet method. An excellent agreement is obtained with recent experimental data [D. M. Neumark, Phys. Chem. Chem. Phys. 7, 433 (2005)] for high electron kinetic energies where only the triplet electronic states contribute. (c) 2006 American Institute of Physics.AIP Publishing202620262006info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10366/169555reponame:GREDOS. Repositorio Institucional de la Universidad de Salamancainstname:Universidad de Salamanca (USAL)InglésAttribution-NonCommercial-NoDerivatives 4.0 Internacionalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:gredos.usal.es:10366/1695552026-06-07T06:28:51Z
dc.title.none.fl_str_mv Coupled diabatic potential energy surfaces for studying the nonadiabatic dynamics at conical intersections in angular resolved photodetachment simulations of OHF−→OHF+e−
title Coupled diabatic potential energy surfaces for studying the nonadiabatic dynamics at conical intersections in angular resolved photodetachment simulations of OHF−→OHF+e−
spellingShingle Coupled diabatic potential energy surfaces for studying the nonadiabatic dynamics at conical intersections in angular resolved photodetachment simulations of OHF−→OHF+e−
Gómez Carrasco, Susana Raquel
Transition state dynamics
Electronic states
Born Oppenheimer
Rate constant
OHF
title_short Coupled diabatic potential energy surfaces for studying the nonadiabatic dynamics at conical intersections in angular resolved photodetachment simulations of OHF−→OHF+e−
title_full Coupled diabatic potential energy surfaces for studying the nonadiabatic dynamics at conical intersections in angular resolved photodetachment simulations of OHF−→OHF+e−
title_fullStr Coupled diabatic potential energy surfaces for studying the nonadiabatic dynamics at conical intersections in angular resolved photodetachment simulations of OHF−→OHF+e−
title_full_unstemmed Coupled diabatic potential energy surfaces for studying the nonadiabatic dynamics at conical intersections in angular resolved photodetachment simulations of OHF−→OHF+e−
title_sort Coupled diabatic potential energy surfaces for studying the nonadiabatic dynamics at conical intersections in angular resolved photodetachment simulations of OHF−→OHF+e−
dc.creator.none.fl_str_mv Gómez Carrasco, Susana Raquel
Aguado, Alfredo
Paniagua, Miguel
Roncero, Octavio
author Gómez Carrasco, Susana Raquel
author_facet Gómez Carrasco, Susana Raquel
Aguado, Alfredo
Paniagua, Miguel
Roncero, Octavio
author_role author
author2 Aguado, Alfredo
Paniagua, Miguel
Roncero, Octavio
author2_role author
author
author
dc.subject.none.fl_str_mv Transition state dynamics
Electronic states
Born Oppenheimer
Rate constant
OHF
topic Transition state dynamics
Electronic states
Born Oppenheimer
Rate constant
OHF
description [EN]An energy-based method is proposed for the diabatization of the OH((2)Pi)+F(P-2)-> O(P-3)+HF((1)Sigma(+)) reaction. It is demonstrated that the diabatic representation obtained is regularized, i.e., the residual derivative couplings do not present singularities at the conical intersections appearing along the reaction path. This method only requires the knowledge of the 1,2 (3)A(') and 1 (3)A(') eigenvalues and does not require any adjustable parameter. Thus, many convergence problems arising in other derivative-based diabatization methods are avoided, and the description of the configuration space along the reaction path is enormously simplified. Three-dimensional coupled diabatic energy surfaces are obtained by an interpolation procedure using approximate to 4000 accurate ab initio points. The angular resolved photodetachment cross sections are obtained in the diabatic and adiabatic representations using a wave packet method. An excellent agreement is obtained with recent experimental data [D. M. Neumark, Phys. Chem. Chem. Phys. 7, 433 (2005)] for high electron kinetic energies where only the triplet electronic states contribute. (c) 2006 American Institute of Physics.
publishDate 2006
dc.date.none.fl_str_mv 2006
2026
2026
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10366/169555
url http://hdl.handle.net/10366/169555
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.rights.none.fl_str_mv Attribution-NonCommercial-NoDerivatives 4.0 Internacional
http://creativecommons.org/licenses/by-nc-nd/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Attribution-NonCommercial-NoDerivatives 4.0 Internacional
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 AIP Publishing
publisher.none.fl_str_mv AIP Publishing
dc.source.none.fl_str_mv reponame:GREDOS. Repositorio Institucional de la Universidad de Salamanca
instname:Universidad de Salamanca (USAL)
instname_str Universidad de Salamanca (USAL)
reponame_str GREDOS. Repositorio Institucional de la Universidad de Salamanca
collection GREDOS. Repositorio Institucional de la Universidad de Salamanca
repository.name.fl_str_mv
repository.mail.fl_str_mv
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