Ab initio 1A' ground potential energy surface and transition state theory kinetics study of the O(1D) + N2O → 2NO, N2 +O2(a1Δg) reactions
An ab initio study of the 1A' ground potential energy surface (PES) of the O(1D) + N2O(X1+) system has been performed at the CASPT2//CASSCF (complete active space second-order perturbation theory//complete active space self-consistent field) level with Pople basis sets. The two reactions leadin...
| Autores: | , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2001 |
| País: | España |
| Institución: | Universidad de Barcelona |
| Repositorio: | Dipòsit Digital de la UB |
| OAI Identifier: | oai:diposit.ub.edu:2445/164273 |
| Acceso en línea: | https://hdl.handle.net/2445/164273 |
| Access Level: | acceso abierto |
| Palabra clave: | Química quàntica Dissociació (Química) Cinètica química Dinàmica Quantum chemistry Dissociation Chemical kinetics Dynamics |
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Ab initio 1A' ground potential energy surface and transition state theory kinetics study of the O(1D) + N2O → 2NO, N2 +O2(a1Δg) reactionsGonzález Pérez, MiguelValero Montero, RosendoAnglada Rull, Josep MariaSayós Ortega, RamónQuímica quànticaDissociació (Química)Cinètica químicaDinàmicaQuantum chemistryDissociationChemical kineticsDynamicsAn ab initio study of the 1A' ground potential energy surface (PES) of the O(1D) + N2O(X1+) system has been performed at the CASPT2//CASSCF (complete active space second-order perturbation theory//complete active space self-consistent field) level with Pople basis sets. The two reactions leading to 2 NO(X2) [reaction (1)] and N2(X1g+) + O2(a1∆g) [reaction (2)] products have been investigated. In both reactions a trans-approach of the attacking oxygen to the N2O moiety is found to be preferred, more markedly in reaction (1). For this reaction also a cis-path is feasible and is possibly connected with the trans -path by a transition state placed below reactants. A thorough characterization of the entrance zone has been performed to allow for subsequent kinetics calculations. Fixed angle and minimum energy paths have been constructed and transition state geometries have been refined at the CASPT2 level, thus obtaining approximate structures and frequencies for the latter. From these calculations it can be inferred that both reactions proceed without an energy barrier. Rate constant calculations in the 100-1000 K temperature range based on CASPT2 structures and using the transition state theory yield values in good agreement with experiment for the two reactions, especially when a proper scaling of the energy barriers is performed. Also, for comparative purposes quasiclassical trajectory calculations were performed on reaction (1) in the same temperature range, using a previous pseudotriatomic analytical potential energy surface, obtaining good agreement with experiment.American Institute of Physics2001info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttps://hdl.handle.net/2445/164273Articles publicats en revistes (Ciència dels Materials i Química Física)reponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglésReproducció del document publicat a: https://doi.org/10.1063/1.1398101Journal of Chemical Physics, 2001, vol. 115, p. 7015-7031https://doi.org/10.1063/1.1398101(c) American Institute of Physics , 2001info:eu-repo/semantics/openAccessoai:diposit.ub.edu:2445/1642732026-05-27T06:46:51Z |
| dc.title.none.fl_str_mv |
Ab initio 1A' ground potential energy surface and transition state theory kinetics study of the O(1D) + N2O → 2NO, N2 +O2(a1Δg) reactions |
| title |
Ab initio 1A' ground potential energy surface and transition state theory kinetics study of the O(1D) + N2O → 2NO, N2 +O2(a1Δg) reactions |
| spellingShingle |
Ab initio 1A' ground potential energy surface and transition state theory kinetics study of the O(1D) + N2O → 2NO, N2 +O2(a1Δg) reactions González Pérez, Miguel Química quàntica Dissociació (Química) Cinètica química Dinàmica Quantum chemistry Dissociation Chemical kinetics Dynamics |
| title_short |
Ab initio 1A' ground potential energy surface and transition state theory kinetics study of the O(1D) + N2O → 2NO, N2 +O2(a1Δg) reactions |
| title_full |
Ab initio 1A' ground potential energy surface and transition state theory kinetics study of the O(1D) + N2O → 2NO, N2 +O2(a1Δg) reactions |
| title_fullStr |
Ab initio 1A' ground potential energy surface and transition state theory kinetics study of the O(1D) + N2O → 2NO, N2 +O2(a1Δg) reactions |
| title_full_unstemmed |
Ab initio 1A' ground potential energy surface and transition state theory kinetics study of the O(1D) + N2O → 2NO, N2 +O2(a1Δg) reactions |
| title_sort |
Ab initio 1A' ground potential energy surface and transition state theory kinetics study of the O(1D) + N2O → 2NO, N2 +O2(a1Δg) reactions |
| dc.creator.none.fl_str_mv |
González Pérez, Miguel Valero Montero, Rosendo Anglada Rull, Josep Maria Sayós Ortega, Ramón |
| author |
González Pérez, Miguel |
| author_facet |
González Pérez, Miguel Valero Montero, Rosendo Anglada Rull, Josep Maria Sayós Ortega, Ramón |
| author_role |
author |
| author2 |
Valero Montero, Rosendo Anglada Rull, Josep Maria Sayós Ortega, Ramón |
| author2_role |
author author author |
| dc.subject.none.fl_str_mv |
Química quàntica Dissociació (Química) Cinètica química Dinàmica Quantum chemistry Dissociation Chemical kinetics Dynamics |
| topic |
Química quàntica Dissociació (Química) Cinètica química Dinàmica Quantum chemistry Dissociation Chemical kinetics Dynamics |
| description |
An ab initio study of the 1A' ground potential energy surface (PES) of the O(1D) + N2O(X1+) system has been performed at the CASPT2//CASSCF (complete active space second-order perturbation theory//complete active space self-consistent field) level with Pople basis sets. The two reactions leading to 2 NO(X2) [reaction (1)] and N2(X1g+) + O2(a1∆g) [reaction (2)] products have been investigated. In both reactions a trans-approach of the attacking oxygen to the N2O moiety is found to be preferred, more markedly in reaction (1). For this reaction also a cis-path is feasible and is possibly connected with the trans -path by a transition state placed below reactants. A thorough characterization of the entrance zone has been performed to allow for subsequent kinetics calculations. Fixed angle and minimum energy paths have been constructed and transition state geometries have been refined at the CASPT2 level, thus obtaining approximate structures and frequencies for the latter. From these calculations it can be inferred that both reactions proceed without an energy barrier. Rate constant calculations in the 100-1000 K temperature range based on CASPT2 structures and using the transition state theory yield values in good agreement with experiment for the two reactions, especially when a proper scaling of the energy barriers is performed. Also, for comparative purposes quasiclassical trajectory calculations were performed on reaction (1) in the same temperature range, using a previous pseudotriatomic analytical potential energy surface, obtaining good agreement with experiment. |
| publishDate |
2001 |
| dc.date.none.fl_str_mv |
2001 |
| 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/2445/164273 |
| url |
https://hdl.handle.net/2445/164273 |
| 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/10.1063/1.1398101 Journal of Chemical Physics, 2001, vol. 115, p. 7015-7031 https://doi.org/10.1063/1.1398101 |
| dc.rights.none.fl_str_mv |
(c) American Institute of Physics , 2001 info:eu-repo/semantics/openAccess |
| rights_invalid_str_mv |
(c) American Institute of Physics , 2001 |
| eu_rights_str_mv |
openAccess |
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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:Dipòsit Digital de la UB instname:Universidad de Barcelona |
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Universidad de Barcelona |
| reponame_str |
Dipòsit Digital de la UB |
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Dipòsit Digital de la UB |
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15,300719 |