Reactive scattering of H2 from Cu(100): comparison of dynamics calculations based on the specific reaction parameter approach to density functional theory with experiment

Autores
Sementa, L.; Wijzenbroek, M.; Van Kolck, B. J.; Somers, M. F.; Al-Halabi, A.; Busnengo, Heriberto Fabio; Olsen, R. A.; Kroes, G. J.; Rutkowski, M.; Thewes, C.; Kleimeier, N. F.; Zacharias, H.
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We present new experimental and theoretical results for reactive scattering of dihydrogen from Cu(100). In the new experiments, the associative desorption of H2 is studied in a velocity resolved and final rovibrational state selected manner, using time-of-flight techniques in combination with resonance-enhanced multi-photon ionization laser detection. Average desorption energies and rota- tional quadrupole alignment parameters were obtained in this way for a number of (v = 0, 1) ro- tational states, v being the vibrational quantum number. Results of quantum dynamics calculations based on a potential energy surface computed with a specific reaction parameter (SRP) density func- tional, which was derived earlier for dihydrogen interacting with Cu(111), are compared with the results of the new experiments and with the results of previous molecular beam experiments on sticking of H2 and on rovibrationally elastic and inelastic scattering of H2 and D2 from Cu(100). The calculations use the Born-Oppenheimer and static surface approximations. With the functional derived semi-empirically for dihydrogen + Cu(111), a chemically accurate description is obtained of the molecular beam experiments on sticking of H2 on Cu(100), and a highly accurate descrip- tion is obtained of rovibrationally elastic and inelastic scattering of D2 from Cu(100) and of the orientational dependence of the reaction of (v = 1, j = 2 − 4) H2 on Cu(100). This suggests that a SRP density functional derived for H2 interacting with a specific low index face of a metal will yield accurate results for H2 reactively scattering from another low index face of the same metal, and that it may also yield accurate results for H2 interacting with a defected (e.g., stepped) surface of that same metal, in a system of catalytic interest. However, the description that was obtained of the average desorption energies, of rovibrationally elastic and inelastic scattering of H2 from Cu(100), and of the orientational dependence of reaction of (v = 0, j = 3 − 5, 8) H2 on Cu(100) compares less well with the available experiments. More research is needed to establish whether more accurate SRP-density functional theory dynamics results can be obtained for these observables if surface atom motion is added to the dynamical model. The experimentally and theoretically found dependence of the rotational quadrupole alignment parameter on the rotational quantum number provides evidence for rotational enhancement of reaction at low translational energies.
Fil: Sementa, L.. Leiden University; Países Bajos. Istituto per i Processi Chimico-Fisici of the Consiglio Nazionale delle Ricerche; Italia
Fil: Wijzenbroek, M.. Leiden University; Países Bajos
Fil: Van Kolck, B. J.. Leiden University; Países Bajos
Fil: Somers, M. F.. Leiden University; Países Bajos
Fil: Al-Halabi, A.. Leiden University; Países Bajos
Fil: Busnengo, Heriberto Fabio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Física de Rosario (i); Argentina
Fil: Olsen, R. A.. Leiden University; Países Bajos. SINTEF Materials and Chemistry; Noruega
Fil: Kroes, G. J.. Leiden University; Países Bajos
Fil: Rutkowski, M.. Westfalische Wilhelms Universitat; Alemania
Fil: Thewes, C.. Westfalische Wilhelms Universitat; Alemania
Fil: Kleimeier, N. F.. Westfalische Wilhelms Universitat; Alemania
Fil: Zacharias, H.. Westfalische Wilhelms Universitat; Alemania
Materia
SURFACES
HYDROGEN
DFT
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:11336/5971

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network_name_str CONICET Digital (CONICET)
spelling Reactive scattering of H2 from Cu(100): comparison of dynamics calculations based on the specific reaction parameter approach to density functional theory with experimentSementa, L.Wijzenbroek, M.Van Kolck, B. J.Somers, M. F.Al-Halabi, A.Busnengo, Heriberto FabioOlsen, R. A.Kroes, G. J.Rutkowski, M.Thewes, C.Kleimeier, N. F.Zacharias, H.SURFACESHYDROGENDFThttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1We present new experimental and theoretical results for reactive scattering of dihydrogen from Cu(100). In the new experiments, the associative desorption of H2 is studied in a velocity resolved and final rovibrational state selected manner, using time-of-flight techniques in combination with resonance-enhanced multi-photon ionization laser detection. Average desorption energies and rota- tional quadrupole alignment parameters were obtained in this way for a number of (v = 0, 1) ro- tational states, v being the vibrational quantum number. Results of quantum dynamics calculations based on a potential energy surface computed with a specific reaction parameter (SRP) density func- tional, which was derived earlier for dihydrogen interacting with Cu(111), are compared with the results of the new experiments and with the results of previous molecular beam experiments on sticking of H2 and on rovibrationally elastic and inelastic scattering of H2 and D2 from Cu(100). The calculations use the Born-Oppenheimer and static surface approximations. With the functional derived semi-empirically for dihydrogen + Cu(111), a chemically accurate description is obtained of the molecular beam experiments on sticking of H2 on Cu(100), and a highly accurate descrip- tion is obtained of rovibrationally elastic and inelastic scattering of D2 from Cu(100) and of the orientational dependence of the reaction of (v = 1, j = 2 − 4) H2 on Cu(100). This suggests that a SRP density functional derived for H2 interacting with a specific low index face of a metal will yield accurate results for H2 reactively scattering from another low index face of the same metal, and that it may also yield accurate results for H2 interacting with a defected (e.g., stepped) surface of that same metal, in a system of catalytic interest. However, the description that was obtained of the average desorption energies, of rovibrationally elastic and inelastic scattering of H2 from Cu(100), and of the orientational dependence of reaction of (v = 0, j = 3 − 5, 8) H2 on Cu(100) compares less well with the available experiments. More research is needed to establish whether more accurate SRP-density functional theory dynamics results can be obtained for these observables if surface atom motion is added to the dynamical model. The experimentally and theoretically found dependence of the rotational quadrupole alignment parameter on the rotational quantum number provides evidence for rotational enhancement of reaction at low translational energies.Fil: Sementa, L.. Leiden University; Países Bajos. Istituto per i Processi Chimico-Fisici of the Consiglio Nazionale delle Ricerche; ItaliaFil: Wijzenbroek, M.. Leiden University; Países BajosFil: Van Kolck, B. J.. Leiden University; Países BajosFil: Somers, M. F.. Leiden University; Países BajosFil: Al-Halabi, A.. Leiden University; Países BajosFil: Busnengo, Heriberto Fabio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Física de Rosario (i); ArgentinaFil: Olsen, R. A.. Leiden University; Países Bajos. SINTEF Materials and Chemistry; NoruegaFil: Kroes, G. J.. Leiden University; Países BajosFil: Rutkowski, M.. Westfalische Wilhelms Universitat; AlemaniaFil: Thewes, C.. Westfalische Wilhelms Universitat; AlemaniaFil: Kleimeier, N. F.. Westfalische Wilhelms Universitat; AlemaniaFil: Zacharias, H.. Westfalische Wilhelms Universitat; AlemaniaAmerican Institute of Physics2013-01-25info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/5971Sementa, L.; Wijzenbroek, M.; Van Kolck, B. J.; Somers, M. F.; Al-Halabi, A.; et al.; Reactive scattering of H2 from Cu(100): comparison of dynamics calculations based on the specific reaction parameter approach to density functional theory with experiment; American Institute of Physics; Journal of Chemical Physics; 138; 4; 25-1-2013; 44708-447270021-9606enginfo:eu-repo/semantics/altIdentifier/doi/info:eu-repo/semantics/altIdentifier/doi/10.1063/1.4776224info:eu-repo/semantics/altIdentifier/url/http://scitation.aip.org/content/aip/journal/jcp/138/4/10.1063/1.4776224info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:15:49Zoai:ri.conicet.gov.ar:11336/5971instacron: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 10:15:49.433CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Reactive scattering of H2 from Cu(100): comparison of dynamics calculations based on the specific reaction parameter approach to density functional theory with experiment
title Reactive scattering of H2 from Cu(100): comparison of dynamics calculations based on the specific reaction parameter approach to density functional theory with experiment
spellingShingle Reactive scattering of H2 from Cu(100): comparison of dynamics calculations based on the specific reaction parameter approach to density functional theory with experiment
Sementa, L.
SURFACES
HYDROGEN
DFT
title_short Reactive scattering of H2 from Cu(100): comparison of dynamics calculations based on the specific reaction parameter approach to density functional theory with experiment
title_full Reactive scattering of H2 from Cu(100): comparison of dynamics calculations based on the specific reaction parameter approach to density functional theory with experiment
title_fullStr Reactive scattering of H2 from Cu(100): comparison of dynamics calculations based on the specific reaction parameter approach to density functional theory with experiment
title_full_unstemmed Reactive scattering of H2 from Cu(100): comparison of dynamics calculations based on the specific reaction parameter approach to density functional theory with experiment
title_sort Reactive scattering of H2 from Cu(100): comparison of dynamics calculations based on the specific reaction parameter approach to density functional theory with experiment
dc.creator.none.fl_str_mv Sementa, L.
Wijzenbroek, M.
Van Kolck, B. J.
Somers, M. F.
Al-Halabi, A.
Busnengo, Heriberto Fabio
Olsen, R. A.
Kroes, G. J.
Rutkowski, M.
Thewes, C.
Kleimeier, N. F.
Zacharias, H.
author Sementa, L.
author_facet Sementa, L.
Wijzenbroek, M.
Van Kolck, B. J.
Somers, M. F.
Al-Halabi, A.
Busnengo, Heriberto Fabio
Olsen, R. A.
Kroes, G. J.
Rutkowski, M.
Thewes, C.
Kleimeier, N. F.
Zacharias, H.
author_role author
author2 Wijzenbroek, M.
Van Kolck, B. J.
Somers, M. F.
Al-Halabi, A.
Busnengo, Heriberto Fabio
Olsen, R. A.
Kroes, G. J.
Rutkowski, M.
Thewes, C.
Kleimeier, N. F.
Zacharias, H.
author2_role author
author
author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv SURFACES
HYDROGEN
DFT
topic SURFACES
HYDROGEN
DFT
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We present new experimental and theoretical results for reactive scattering of dihydrogen from Cu(100). In the new experiments, the associative desorption of H2 is studied in a velocity resolved and final rovibrational state selected manner, using time-of-flight techniques in combination with resonance-enhanced multi-photon ionization laser detection. Average desorption energies and rota- tional quadrupole alignment parameters were obtained in this way for a number of (v = 0, 1) ro- tational states, v being the vibrational quantum number. Results of quantum dynamics calculations based on a potential energy surface computed with a specific reaction parameter (SRP) density func- tional, which was derived earlier for dihydrogen interacting with Cu(111), are compared with the results of the new experiments and with the results of previous molecular beam experiments on sticking of H2 and on rovibrationally elastic and inelastic scattering of H2 and D2 from Cu(100). The calculations use the Born-Oppenheimer and static surface approximations. With the functional derived semi-empirically for dihydrogen + Cu(111), a chemically accurate description is obtained of the molecular beam experiments on sticking of H2 on Cu(100), and a highly accurate descrip- tion is obtained of rovibrationally elastic and inelastic scattering of D2 from Cu(100) and of the orientational dependence of the reaction of (v = 1, j = 2 − 4) H2 on Cu(100). This suggests that a SRP density functional derived for H2 interacting with a specific low index face of a metal will yield accurate results for H2 reactively scattering from another low index face of the same metal, and that it may also yield accurate results for H2 interacting with a defected (e.g., stepped) surface of that same metal, in a system of catalytic interest. However, the description that was obtained of the average desorption energies, of rovibrationally elastic and inelastic scattering of H2 from Cu(100), and of the orientational dependence of reaction of (v = 0, j = 3 − 5, 8) H2 on Cu(100) compares less well with the available experiments. More research is needed to establish whether more accurate SRP-density functional theory dynamics results can be obtained for these observables if surface atom motion is added to the dynamical model. The experimentally and theoretically found dependence of the rotational quadrupole alignment parameter on the rotational quantum number provides evidence for rotational enhancement of reaction at low translational energies.
Fil: Sementa, L.. Leiden University; Países Bajos. Istituto per i Processi Chimico-Fisici of the Consiglio Nazionale delle Ricerche; Italia
Fil: Wijzenbroek, M.. Leiden University; Países Bajos
Fil: Van Kolck, B. J.. Leiden University; Países Bajos
Fil: Somers, M. F.. Leiden University; Países Bajos
Fil: Al-Halabi, A.. Leiden University; Países Bajos
Fil: Busnengo, Heriberto Fabio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Física de Rosario (i); Argentina
Fil: Olsen, R. A.. Leiden University; Países Bajos. SINTEF Materials and Chemistry; Noruega
Fil: Kroes, G. J.. Leiden University; Países Bajos
Fil: Rutkowski, M.. Westfalische Wilhelms Universitat; Alemania
Fil: Thewes, C.. Westfalische Wilhelms Universitat; Alemania
Fil: Kleimeier, N. F.. Westfalische Wilhelms Universitat; Alemania
Fil: Zacharias, H.. Westfalische Wilhelms Universitat; Alemania
description We present new experimental and theoretical results for reactive scattering of dihydrogen from Cu(100). In the new experiments, the associative desorption of H2 is studied in a velocity resolved and final rovibrational state selected manner, using time-of-flight techniques in combination with resonance-enhanced multi-photon ionization laser detection. Average desorption energies and rota- tional quadrupole alignment parameters were obtained in this way for a number of (v = 0, 1) ro- tational states, v being the vibrational quantum number. Results of quantum dynamics calculations based on a potential energy surface computed with a specific reaction parameter (SRP) density func- tional, which was derived earlier for dihydrogen interacting with Cu(111), are compared with the results of the new experiments and with the results of previous molecular beam experiments on sticking of H2 and on rovibrationally elastic and inelastic scattering of H2 and D2 from Cu(100). The calculations use the Born-Oppenheimer and static surface approximations. With the functional derived semi-empirically for dihydrogen + Cu(111), a chemically accurate description is obtained of the molecular beam experiments on sticking of H2 on Cu(100), and a highly accurate descrip- tion is obtained of rovibrationally elastic and inelastic scattering of D2 from Cu(100) and of the orientational dependence of the reaction of (v = 1, j = 2 − 4) H2 on Cu(100). This suggests that a SRP density functional derived for H2 interacting with a specific low index face of a metal will yield accurate results for H2 reactively scattering from another low index face of the same metal, and that it may also yield accurate results for H2 interacting with a defected (e.g., stepped) surface of that same metal, in a system of catalytic interest. However, the description that was obtained of the average desorption energies, of rovibrationally elastic and inelastic scattering of H2 from Cu(100), and of the orientational dependence of reaction of (v = 0, j = 3 − 5, 8) H2 on Cu(100) compares less well with the available experiments. More research is needed to establish whether more accurate SRP-density functional theory dynamics results can be obtained for these observables if surface atom motion is added to the dynamical model. The experimentally and theoretically found dependence of the rotational quadrupole alignment parameter on the rotational quantum number provides evidence for rotational enhancement of reaction at low translational energies.
publishDate 2013
dc.date.none.fl_str_mv 2013-01-25
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/11336/5971
Sementa, L.; Wijzenbroek, M.; Van Kolck, B. J.; Somers, M. F.; Al-Halabi, A.; et al.; Reactive scattering of H2 from Cu(100): comparison of dynamics calculations based on the specific reaction parameter approach to density functional theory with experiment; American Institute of Physics; Journal of Chemical Physics; 138; 4; 25-1-2013; 44708-44727
0021-9606
url http://hdl.handle.net/11336/5971
identifier_str_mv Sementa, L.; Wijzenbroek, M.; Van Kolck, B. J.; Somers, M. F.; Al-Halabi, A.; et al.; Reactive scattering of H2 from Cu(100): comparison of dynamics calculations based on the specific reaction parameter approach to density functional theory with experiment; American Institute of Physics; Journal of Chemical Physics; 138; 4; 25-1-2013; 44708-44727
0021-9606
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/
info:eu-repo/semantics/altIdentifier/doi/10.1063/1.4776224
info:eu-repo/semantics/altIdentifier/url/http://scitation.aip.org/content/aip/journal/jcp/138/4/10.1063/1.4776224
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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