Ab initio ground potential energy surface and quasiclassical trajectory study of the O(1D)+CH4(X1A1)→OH(X 2Π)+CH3(X 2A ″2) reaction dynamics
An ab initio study of the ground potential energy surface (PES) of the O(1D)+CH4→OH+CH3 reaction has been performed using the second and fourth order Møller-Plesset methods with a large basis set. From the ab initio data a triatomic analytical ground PES with the methyl group treated as an atom of 1...
| Autores: | , , , |
|---|---|
| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 1999 |
| País: | España |
| Institución: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositorio: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:2445/164250 |
| Acceso en línea: | https://hdl.handle.net/2445/164250 |
| Access Level: | acceso abierto |
| Palabra clave: | Química quàntica Dissociació (Química) Química física Quantum chemistry Dissociation Physical and theoretical chemistry |
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Ab initio ground potential energy surface and quasiclassical trajectory study of the O(1D)+CH4(X1A1)→OH(X 2Π)+CH3(X 2A ″2) reaction dynamicsGonzález Pérez, MiguelHernando, JordiBaños, IreneSayós Ortega, RamónQuímica quànticaDissociació (Química)Química físicaQuantum chemistryDissociationPhysical and theoretical chemistryAn ab initio study of the ground potential energy surface (PES) of the O(1D)+CH4→OH+CH3 reaction has been performed using the second and fourth order Møller-Plesset methods with a large basis set. From the ab initio data a triatomic analytical ground PES with the methyl group treated as an atom of 15.0 amu has been derived. This PES has been employed to study the dynamics of the reaction by means of the quasiclassical trajectory (QCT) method. A good agreement between the experimental and QCT OH rovibrational distributions at a collision energy of 0.212 eV with the methane molecule at 298 K has been obtained. The analysis of the microscopic reaction mechanism shows that the reaction takes place almost exclusively through the insertion of the O(1D) atom into a C-H bond, due to the presence of the deep (CH3)OH minimum, and the resulting trajectories may be direct or nondirect (short-lived collision complexes mainly) with about the same probability. The OH vibrational distribution arising from the direct mechanism is inverted, while the nondirect mechanism leads to a noninverted one. There is some tendency to give broader OH rotational distributions peaking at higher N′ values, particularly for the vibrational levels v′ = 0-1, in the case of the nondirect trajectories. The PES derived here may be used in dynamics studies under conditions where the methyl group motions are not strongly coupled to the motions leading to reaction.American Institute of Physics2020202019992020info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersion12 p.application/pdfhttps://hdl.handle.net/2445/164250Articles publicats en revistes (Ciència dels Materials i Química Física)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésReproducció del document publicat a: https://doi.org/10.1063/1.480236Journal of Chemical Physics, 1999, vol. 111, num. 19, p. 8913-8924https://doi.org/10.1063/1.480236(c) American Institute of Physics , 1999info:eu-repo/semantics/openAccessoai:recercat.cat:2445/1642502026-05-29T05:05:01Z |
| dc.title.none.fl_str_mv |
Ab initio ground potential energy surface and quasiclassical trajectory study of the O(1D)+CH4(X1A1)→OH(X 2Π)+CH3(X 2A ″2) reaction dynamics |
| title |
Ab initio ground potential energy surface and quasiclassical trajectory study of the O(1D)+CH4(X1A1)→OH(X 2Π)+CH3(X 2A ″2) reaction dynamics |
| spellingShingle |
Ab initio ground potential energy surface and quasiclassical trajectory study of the O(1D)+CH4(X1A1)→OH(X 2Π)+CH3(X 2A ″2) reaction dynamics González Pérez, Miguel Química quàntica Dissociació (Química) Química física Quantum chemistry Dissociation Physical and theoretical chemistry |
| title_short |
Ab initio ground potential energy surface and quasiclassical trajectory study of the O(1D)+CH4(X1A1)→OH(X 2Π)+CH3(X 2A ″2) reaction dynamics |
| title_full |
Ab initio ground potential energy surface and quasiclassical trajectory study of the O(1D)+CH4(X1A1)→OH(X 2Π)+CH3(X 2A ″2) reaction dynamics |
| title_fullStr |
Ab initio ground potential energy surface and quasiclassical trajectory study of the O(1D)+CH4(X1A1)→OH(X 2Π)+CH3(X 2A ″2) reaction dynamics |
| title_full_unstemmed |
Ab initio ground potential energy surface and quasiclassical trajectory study of the O(1D)+CH4(X1A1)→OH(X 2Π)+CH3(X 2A ″2) reaction dynamics |
| title_sort |
Ab initio ground potential energy surface and quasiclassical trajectory study of the O(1D)+CH4(X1A1)→OH(X 2Π)+CH3(X 2A ″2) reaction dynamics |
| dc.creator.none.fl_str_mv |
González Pérez, Miguel Hernando, Jordi Baños, Irene Sayós Ortega, Ramón |
| author |
González Pérez, Miguel |
| author_facet |
González Pérez, Miguel Hernando, Jordi Baños, Irene Sayós Ortega, Ramón |
| author_role |
author |
| author2 |
Hernando, Jordi Baños, Irene Sayós Ortega, Ramón |
| author2_role |
author author author |
| dc.subject.none.fl_str_mv |
Química quàntica Dissociació (Química) Química física Quantum chemistry Dissociation Physical and theoretical chemistry |
| topic |
Química quàntica Dissociació (Química) Química física Quantum chemistry Dissociation Physical and theoretical chemistry |
| description |
An ab initio study of the ground potential energy surface (PES) of the O(1D)+CH4→OH+CH3 reaction has been performed using the second and fourth order Møller-Plesset methods with a large basis set. From the ab initio data a triatomic analytical ground PES with the methyl group treated as an atom of 15.0 amu has been derived. This PES has been employed to study the dynamics of the reaction by means of the quasiclassical trajectory (QCT) method. A good agreement between the experimental and QCT OH rovibrational distributions at a collision energy of 0.212 eV with the methane molecule at 298 K has been obtained. The analysis of the microscopic reaction mechanism shows that the reaction takes place almost exclusively through the insertion of the O(1D) atom into a C-H bond, due to the presence of the deep (CH3)OH minimum, and the resulting trajectories may be direct or nondirect (short-lived collision complexes mainly) with about the same probability. The OH vibrational distribution arising from the direct mechanism is inverted, while the nondirect mechanism leads to a noninverted one. There is some tendency to give broader OH rotational distributions peaking at higher N′ values, particularly for the vibrational levels v′ = 0-1, in the case of the nondirect trajectories. The PES derived here may be used in dynamics studies under conditions where the methyl group motions are not strongly coupled to the motions leading to reaction. |
| publishDate |
1999 |
| dc.date.none.fl_str_mv |
1999 2020 2020 2020 |
| 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 |
https://hdl.handle.net/2445/164250 |
| url |
https://hdl.handle.net/2445/164250 |
| dc.language.none.fl_str_mv |
Inglés |
| language_invalid_str_mv |
Inglés |
| dc.relation.none.fl_str_mv |
Reproducció del document publicat a: https://doi.org/10.1063/1.480236 Journal of Chemical Physics, 1999, vol. 111, num. 19, p. 8913-8924 https://doi.org/10.1063/1.480236 |
| dc.rights.none.fl_str_mv |
(c) American Institute of Physics , 1999 info:eu-repo/semantics/openAccess |
| rights_invalid_str_mv |
(c) American Institute of Physics , 1999 |
| eu_rights_str_mv |
openAccess |
| dc.format.none.fl_str_mv |
12 p. 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 |
Articles publicats en revistes (Ciència dels Materials i Química Física) reponame:Recercat. Dipósit de la Recerca de Catalunya instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| instname_str |
Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| reponame_str |
Recercat. Dipósit de la Recerca de Catalunya |
| collection |
Recercat. Dipósit de la Recerca de Catalunya |
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1869420555378098176 |
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15,811543 |