## Abstract

A reduced dimensionality quantum scattering method is extended to the study of spin-orbit nonadiabatic transitions in the CH3 + HCl reversible arrow CH4 + Cl(P-2(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. (C) 2011 American Institute of Physics. [doi:10.1063/1.3592732]

Original language | English |
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Article number | 204311 |

Pages (from-to) | - |

Number of pages | 15 |

Journal | Journal of Chemical Physics |

Volume | 134 |

Issue number | 20 |

DOIs | |

Publication status | Published - 28 May 2011 |