Product lambda-doublet ratios as an imprint of chemical reaction mechanism
In the last decade, the development of theoretical methods has allowed chemists to reproduce and explain almost all of the experimental data associated with elementary atom plus diatom collisions. However, there are still a few examples where theory cannot account yet for experimental results. This...
| Auteurs principaux: | , , , , |
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| Format: | Journal article |
| Langue: | English |
| Publié: |
Nature Publishing Group
2016
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| _version_ | 1826306864035397632 |
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| author | Jambrina, P Zanchet, A Aldegunde, J Brouard, M Aoiz, F |
| author_facet | Jambrina, P Zanchet, A Aldegunde, J Brouard, M Aoiz, F |
| author_sort | Jambrina, P |
| collection | OXFORD |
| description | In the last decade, the development of theoretical methods has allowed chemists to reproduce and explain almost all of the experimental data associated with elementary atom plus diatom collisions. However, there are still a few examples where theory cannot account yet for experimental results. This is the case for the preferential population of one of the Λ-doublet states produced by chemical reactions. In particular, recent measurements of the OD((2)Π) product of the O((3)P)+D2 reaction have shown a clear preference for the Π(A') Λ-doublet states, in apparent contradiction with ab initio calculations, which predict a larger reactivity on the A'' potential energy surface. Here we present a method to calculate the Λ-doublet ratio when concurrent potential energy surfaces participate in the reaction. It accounts for the experimental Λ-doublet populations via explicit consideration of the stereodynamics of the process. Furthermore, our results demonstrate that the propensity of the Π(A') state is a consequence of the different mechanisms of the reaction on the two concurrent potential energy surfaces. |
| first_indexed | 2024-03-07T06:54:21Z |
| format | Journal article |
| id | oxford-uuid:fd9d0fd8-01d2-4876-826d-029327bbeb5c |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T06:54:21Z |
| publishDate | 2016 |
| publisher | Nature Publishing Group |
| record_format | dspace |
| spelling | oxford-uuid:fd9d0fd8-01d2-4876-826d-029327bbeb5c2022-03-27T13:30:09ZProduct lambda-doublet ratios as an imprint of chemical reaction mechanismJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:fd9d0fd8-01d2-4876-826d-029327bbeb5cEnglishSymplectic Elements at OxfordNature Publishing Group2016Jambrina, PZanchet, AAldegunde, JBrouard, MAoiz, FIn the last decade, the development of theoretical methods has allowed chemists to reproduce and explain almost all of the experimental data associated with elementary atom plus diatom collisions. However, there are still a few examples where theory cannot account yet for experimental results. This is the case for the preferential population of one of the Λ-doublet states produced by chemical reactions. In particular, recent measurements of the OD((2)Π) product of the O((3)P)+D2 reaction have shown a clear preference for the Π(A') Λ-doublet states, in apparent contradiction with ab initio calculations, which predict a larger reactivity on the A'' potential energy surface. Here we present a method to calculate the Λ-doublet ratio when concurrent potential energy surfaces participate in the reaction. It accounts for the experimental Λ-doublet populations via explicit consideration of the stereodynamics of the process. Furthermore, our results demonstrate that the propensity of the Π(A') state is a consequence of the different mechanisms of the reaction on the two concurrent potential energy surfaces. |
| spellingShingle | Jambrina, P Zanchet, A Aldegunde, J Brouard, M Aoiz, F Product lambda-doublet ratios as an imprint of chemical reaction mechanism |
| title | Product lambda-doublet ratios as an imprint of chemical reaction mechanism |
| title_full | Product lambda-doublet ratios as an imprint of chemical reaction mechanism |
| title_fullStr | Product lambda-doublet ratios as an imprint of chemical reaction mechanism |
| title_full_unstemmed | Product lambda-doublet ratios as an imprint of chemical reaction mechanism |
| title_short | Product lambda-doublet ratios as an imprint of chemical reaction mechanism |
| title_sort | product lambda doublet ratios as an imprint of chemical reaction mechanism |
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