An investigation of the F+H-2 reaction based on a full ab initio description of the open-shell character of the F(P-2) atom
Expanding on an earlier Communication [M. H. Alexander, H.-J. Werner, and D. E. Manolopoulos, J. Chem. Phys. 109, 5710 (1998)], we present here the full framework for the quantum treatment of . reactions of the fluorine atom with molecular hydrogen. This involves four potential energy surfaces (PESs...
| Main Authors: | , , |
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| Formato: | Journal article |
| Idioma: | English |
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2000
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| _version_ | 1826265138052726784 |
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| author | Alexander, M Manolopoulos, D Werner, H |
| author_facet | Alexander, M Manolopoulos, D Werner, H |
| author_sort | Alexander, M |
| collection | OXFORD |
| description | Expanding on an earlier Communication [M. H. Alexander, H.-J. Werner, and D. E. Manolopoulos, J. Chem. Phys. 109, 5710 (1998)], we present here the full framework for the quantum treatment of . reactions of the fluorine atom with molecular hydrogen. This involves four potential energy surfaces (PESs) and two, coordinate-dependent spin-orbit interaction terms, all of which were fitted to the results of ab initio calculations. Quantum scattering calculations, based on a time-independent method formulated in hyperspherical coordinates, were carried out to determine initial and final state-resolved reactive cross sections, for reaction of F in its ground (2P3/2) and excited (2P1/2) spin-orbit state with H2 in j = 0 and j = 2(pH2) and j = 1(oH2). The overall reactivity of the excited state of F, which can occur only through nonadiabatic transitions, is found to be small, at most 25% of the reactivity of the ground spin-orbit state, which is adiabatically allowed. In addition, when compared with results of earlier calculations, based on a single, electronically adiabatic, PES, our calculations show that even fine details of the dynamics of the F+H2 reaction will be well described by calculations on a single PES. The contribution of the excited spin-orbit state can be seen most clearly in the formation of HF products in the v = 3 vibrational manifold, which are nearly thermoneutral (or even slightly endoergic) in the reaction of ground-state F atoms. The cross section for the near resonant electronic-rotational process [F* + H2(j = 0) → F+H2(j = 2)] is found to be large, in confirmation of earlier work. © 2000 American Institute of Physics. |
| first_indexed | 2024-03-06T20:18:58Z |
| format | Journal article |
| id | oxford-uuid:2d24b7b5-d18c-49a5-8171-4db92d9a7ca0 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T20:18:58Z |
| publishDate | 2000 |
| record_format | dspace |
| spelling | oxford-uuid:2d24b7b5-d18c-49a5-8171-4db92d9a7ca02022-03-26T12:41:01ZAn investigation of the F+H-2 reaction based on a full ab initio description of the open-shell character of the F(P-2) atomJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:2d24b7b5-d18c-49a5-8171-4db92d9a7ca0EnglishSymplectic Elements at Oxford2000Alexander, MManolopoulos, DWerner, HExpanding on an earlier Communication [M. H. Alexander, H.-J. Werner, and D. E. Manolopoulos, J. Chem. Phys. 109, 5710 (1998)], we present here the full framework for the quantum treatment of . reactions of the fluorine atom with molecular hydrogen. This involves four potential energy surfaces (PESs) and two, coordinate-dependent spin-orbit interaction terms, all of which were fitted to the results of ab initio calculations. Quantum scattering calculations, based on a time-independent method formulated in hyperspherical coordinates, were carried out to determine initial and final state-resolved reactive cross sections, for reaction of F in its ground (2P3/2) and excited (2P1/2) spin-orbit state with H2 in j = 0 and j = 2(pH2) and j = 1(oH2). The overall reactivity of the excited state of F, which can occur only through nonadiabatic transitions, is found to be small, at most 25% of the reactivity of the ground spin-orbit state, which is adiabatically allowed. In addition, when compared with results of earlier calculations, based on a single, electronically adiabatic, PES, our calculations show that even fine details of the dynamics of the F+H2 reaction will be well described by calculations on a single PES. The contribution of the excited spin-orbit state can be seen most clearly in the formation of HF products in the v = 3 vibrational manifold, which are nearly thermoneutral (or even slightly endoergic) in the reaction of ground-state F atoms. The cross section for the near resonant electronic-rotational process [F* + H2(j = 0) → F+H2(j = 2)] is found to be large, in confirmation of earlier work. © 2000 American Institute of Physics. |
| spellingShingle | Alexander, M Manolopoulos, D Werner, H An investigation of the F+H-2 reaction based on a full ab initio description of the open-shell character of the F(P-2) atom |
| title | An investigation of the F+H-2 reaction based on a full ab initio description of the open-shell character of the F(P-2) atom |
| title_full | An investigation of the F+H-2 reaction based on a full ab initio description of the open-shell character of the F(P-2) atom |
| title_fullStr | An investigation of the F+H-2 reaction based on a full ab initio description of the open-shell character of the F(P-2) atom |
| title_full_unstemmed | An investigation of the F+H-2 reaction based on a full ab initio description of the open-shell character of the F(P-2) atom |
| title_short | An investigation of the F+H-2 reaction based on a full ab initio description of the open-shell character of the F(P-2) atom |
| title_sort | investigation of the f h 2 reaction based on a full ab initio description of the open shell character of the f p 2 atom |
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