Reduced dimensionality spin-orbit dynamics of CH3 + HCl ⇌ CH4 + Cl on ab initio surfaces.
A reduced dimensionality quantum scattering method is extended to the study of spin-orbit nonadiabatic transitions in the CH(3) + HCl ⇌ CH(4) + Cl((2)P(J)) reaction. Three two-dimensional potential energy surfaces are developed by fitting a 29 parameter double-Morse function to CCSD(T)/IB//MP2/cc-pV...
| Main Authors: | , , , , |
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| Format: | Journal article |
| Language: | English |
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2011
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| _version_ | 1797069277116760064 |
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| author | Remmert, S Banks, S Harvey, J Orr-Ewing, A Clary, D |
| author_facet | Remmert, S Banks, S Harvey, J Orr-Ewing, A Clary, D |
| author_sort | Remmert, S |
| collection | OXFORD |
| description | A reduced dimensionality quantum scattering method is extended to the study of spin-orbit nonadiabatic transitions in the CH(3) + HCl ⇌ CH(4) + Cl((2)P(J)) reaction. Three two-dimensional potential energy surfaces are developed by fitting a 29 parameter double-Morse function to CCSD(T)/IB//MP2/cc-pV(T+d)Z-dk ab initio data; interaction between surfaces is described by geometry-dependent spin-orbit coupling functions fit to MCSCF/cc-pV(T+d)Z-dk ab initio data. Spectator modes are treated adiabatically via inclusion of curvilinear projected frequencies. The total scattering wave function is expanded in a vibronic basis set and close-coupled equations are solved via R-matrix propagation. Ground state thermal rate constants for forward and reverse reactions agree well with experiment. Multi-surface reaction probabilities, integral cross sections, and initial-state selected branching ratios all highlight the importance of vibrational energy in mediating nonadiabatic transition. Electronically excited state dynamics are seen to play a small but significant role as consistent with experimental conclusions. |
| first_indexed | 2024-03-06T22:22:04Z |
| format | Journal article |
| id | oxford-uuid:556321e3-ddeb-49c6-8dc9-4993237f48c0 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T22:22:04Z |
| publishDate | 2011 |
| record_format | dspace |
| spelling | oxford-uuid:556321e3-ddeb-49c6-8dc9-4993237f48c02022-03-26T16:43:44ZReduced dimensionality spin-orbit dynamics of CH3 + HCl ⇌ CH4 + Cl on ab initio surfaces.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:556321e3-ddeb-49c6-8dc9-4993237f48c0EnglishSymplectic Elements at Oxford2011Remmert, SBanks, SHarvey, JOrr-Ewing, AClary, DA reduced dimensionality quantum scattering method is extended to the study of spin-orbit nonadiabatic transitions in the CH(3) + HCl ⇌ CH(4) + Cl((2)P(J)) reaction. Three two-dimensional potential energy surfaces are developed by fitting a 29 parameter double-Morse function to CCSD(T)/IB//MP2/cc-pV(T+d)Z-dk ab initio data; interaction between surfaces is described by geometry-dependent spin-orbit coupling functions fit to MCSCF/cc-pV(T+d)Z-dk ab initio data. Spectator modes are treated adiabatically via inclusion of curvilinear projected frequencies. The total scattering wave function is expanded in a vibronic basis set and close-coupled equations are solved via R-matrix propagation. Ground state thermal rate constants for forward and reverse reactions agree well with experiment. Multi-surface reaction probabilities, integral cross sections, and initial-state selected branching ratios all highlight the importance of vibrational energy in mediating nonadiabatic transition. Electronically excited state dynamics are seen to play a small but significant role as consistent with experimental conclusions. |
| spellingShingle | Remmert, S Banks, S Harvey, J Orr-Ewing, A Clary, D Reduced dimensionality spin-orbit dynamics of CH3 + HCl ⇌ CH4 + Cl on ab initio surfaces. |
| title | Reduced dimensionality spin-orbit dynamics of CH3 + HCl ⇌ CH4 + Cl on ab initio surfaces. |
| title_full | Reduced dimensionality spin-orbit dynamics of CH3 + HCl ⇌ CH4 + Cl on ab initio surfaces. |
| title_fullStr | Reduced dimensionality spin-orbit dynamics of CH3 + HCl ⇌ CH4 + Cl on ab initio surfaces. |
| title_full_unstemmed | Reduced dimensionality spin-orbit dynamics of CH3 + HCl ⇌ CH4 + Cl on ab initio surfaces. |
| title_short | Reduced dimensionality spin-orbit dynamics of CH3 + HCl ⇌ CH4 + Cl on ab initio surfaces. |
| title_sort | reduced dimensionality spin orbit dynamics of ch3 hcl ⇌ ch4 cl on ab initio surfaces |
| work_keys_str_mv | AT remmerts reduceddimensionalityspinorbitdynamicsofch3hclch4clonabinitiosurfaces AT bankss reduceddimensionalityspinorbitdynamicsofch3hclch4clonabinitiosurfaces AT harveyj reduceddimensionalityspinorbitdynamicsofch3hclch4clonabinitiosurfaces AT orrewinga reduceddimensionalityspinorbitdynamicsofch3hclch4clonabinitiosurfaces AT claryd reduceddimensionalityspinorbitdynamicsofch3hclch4clonabinitiosurfaces |