An improved treatment of spectator mode vibrations in reduced dimensional quantum dynamics: application to the hydrogen abstraction reactions mu + CH4, H + CH4, D + CH4, and CH3 + CH4.
A method for projecting chemical reaction surface coordinates from a Hessian in curvilinear internal coordinates has recently been developed. Here we introduce a modification to this approach which allows for analytical evaluation of the necessary coordinate derivatives, thus reducing the number of...
| Main Authors: | , , , |
|---|---|
| Formato: | Journal article |
| Idioma: | English |
| Publicado: |
2009
|
| _version_ | 1826289966582333440 |
|---|---|
| author | Banks, S Tautermann, C Remmert, S Clary, D |
| author_facet | Banks, S Tautermann, C Remmert, S Clary, D |
| author_sort | Banks, S |
| collection | OXFORD |
| description | A method for projecting chemical reaction surface coordinates from a Hessian in curvilinear internal coordinates has recently been developed. Here we introduce a modification to this approach which allows for analytical evaluation of the necessary coordinate derivatives, thus reducing the number of ab initio calculations required. We apply this method to the determination of spectator mode frequencies and zero-point energies for the series of hydrogen abstraction reactions X + CH(4) --> XH + CH(3), X = muonium (mu), H, D, CH(3). Comparison of these frequencies with those obtained using rectilinear coordinates allows us to examine how the mass of X affects the coordinate sensitivity of the spectator modes. We carry out two-dimensional quantum reactive scattering calculations for these reactions to highlight instances where the choice of coordinates may have a significant impact on the evaluated thermal rate constants. |
| first_indexed | 2024-03-07T02:36:58Z |
| format | Journal article |
| id | oxford-uuid:a91e799c-40b9-428b-b3a4-048cf54fc9a7 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T02:36:58Z |
| publishDate | 2009 |
| record_format | dspace |
| spelling | oxford-uuid:a91e799c-40b9-428b-b3a4-048cf54fc9a72022-03-27T03:06:17ZAn improved treatment of spectator mode vibrations in reduced dimensional quantum dynamics: application to the hydrogen abstraction reactions mu + CH4, H + CH4, D + CH4, and CH3 + CH4.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:a91e799c-40b9-428b-b3a4-048cf54fc9a7EnglishSymplectic Elements at Oxford2009Banks, STautermann, CRemmert, SClary, DA method for projecting chemical reaction surface coordinates from a Hessian in curvilinear internal coordinates has recently been developed. Here we introduce a modification to this approach which allows for analytical evaluation of the necessary coordinate derivatives, thus reducing the number of ab initio calculations required. We apply this method to the determination of spectator mode frequencies and zero-point energies for the series of hydrogen abstraction reactions X + CH(4) --> XH + CH(3), X = muonium (mu), H, D, CH(3). Comparison of these frequencies with those obtained using rectilinear coordinates allows us to examine how the mass of X affects the coordinate sensitivity of the spectator modes. We carry out two-dimensional quantum reactive scattering calculations for these reactions to highlight instances where the choice of coordinates may have a significant impact on the evaluated thermal rate constants. |
| spellingShingle | Banks, S Tautermann, C Remmert, S Clary, D An improved treatment of spectator mode vibrations in reduced dimensional quantum dynamics: application to the hydrogen abstraction reactions mu + CH4, H + CH4, D + CH4, and CH3 + CH4. |
| title | An improved treatment of spectator mode vibrations in reduced dimensional quantum dynamics: application to the hydrogen abstraction reactions mu + CH4, H + CH4, D + CH4, and CH3 + CH4. |
| title_full | An improved treatment of spectator mode vibrations in reduced dimensional quantum dynamics: application to the hydrogen abstraction reactions mu + CH4, H + CH4, D + CH4, and CH3 + CH4. |
| title_fullStr | An improved treatment of spectator mode vibrations in reduced dimensional quantum dynamics: application to the hydrogen abstraction reactions mu + CH4, H + CH4, D + CH4, and CH3 + CH4. |
| title_full_unstemmed | An improved treatment of spectator mode vibrations in reduced dimensional quantum dynamics: application to the hydrogen abstraction reactions mu + CH4, H + CH4, D + CH4, and CH3 + CH4. |
| title_short | An improved treatment of spectator mode vibrations in reduced dimensional quantum dynamics: application to the hydrogen abstraction reactions mu + CH4, H + CH4, D + CH4, and CH3 + CH4. |
| title_sort | improved treatment of spectator mode vibrations in reduced dimensional quantum dynamics application to the hydrogen abstraction reactions mu ch4 h ch4 d ch4 and ch3 ch4 |
| work_keys_str_mv | AT bankss animprovedtreatmentofspectatormodevibrationsinreduceddimensionalquantumdynamicsapplicationtothehydrogenabstractionreactionsmuch4hch4dch4andch3ch4 AT tautermannc animprovedtreatmentofspectatormodevibrationsinreduceddimensionalquantumdynamicsapplicationtothehydrogenabstractionreactionsmuch4hch4dch4andch3ch4 AT remmerts animprovedtreatmentofspectatormodevibrationsinreduceddimensionalquantumdynamicsapplicationtothehydrogenabstractionreactionsmuch4hch4dch4andch3ch4 AT claryd animprovedtreatmentofspectatormodevibrationsinreduceddimensionalquantumdynamicsapplicationtothehydrogenabstractionreactionsmuch4hch4dch4andch3ch4 AT bankss improvedtreatmentofspectatormodevibrationsinreduceddimensionalquantumdynamicsapplicationtothehydrogenabstractionreactionsmuch4hch4dch4andch3ch4 AT tautermannc improvedtreatmentofspectatormodevibrationsinreduceddimensionalquantumdynamicsapplicationtothehydrogenabstractionreactionsmuch4hch4dch4andch3ch4 AT remmerts improvedtreatmentofspectatormodevibrationsinreduceddimensionalquantumdynamicsapplicationtothehydrogenabstractionreactionsmuch4hch4dch4andch3ch4 AT claryd improvedtreatmentofspectatormodevibrationsinreduceddimensionalquantumdynamicsapplicationtothehydrogenabstractionreactionsmuch4hch4dch4andch3ch4 |