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Issue 25, 2007
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Imaging the nonadiabatic dynamics of the CH3 + HCl reaction

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Abstract

LAB-frame velocity distributions of Cl-atoms produced in the photoinitiated reaction of CH3 radicals with HCl have been measured for both the ground Cl (2P3/2) and excited Cl* (2P1/2) spin–orbit states using a DC slice velocity-map ion imaging technique. The similarity of these distributions, as well as the average internal excitation of methane co-products for both Cl and Cl* pathways, suggest that all the reactive flux proceeds through the same transition state on the ground potential energy surface (PES) and that the couplings which promote nonadiabatic transitions to the excited PES correlating to Cl* occur later in the exit channel, beyond the TS region. The nature of these couplings is discussed in light of initial vibrational excitation of CH3 radicals as well as previously reported nonadiabatic reactivity in other polyatomic molecule reactions. Furthermore, the scattering of the reaction products, derived using the photoloc method, suggests that at the high collision energy of our experiment (〈Ecoll〉 = 22.3 kcal mol−1), large impact parameter collisions are favoured with a reduced kinematic constraint on the internal excitation of the methane co-product.

Graphical abstract: Imaging the nonadiabatic dynamics of the CH3 + HCl reaction

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Publication details

The article was received on 23 Mar 2007, accepted on 12 Apr 2007 and first published on 03 May 2007


Article type: Paper
DOI: 10.1039/B704463A
Citation: Phys. Chem. Chem. Phys., 2007,9, 3261-3267
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    Imaging the nonadiabatic dynamics of the CH3 + HCl reaction

    B. Retail, S. J. Greaves, J. K. Pearce, R. A. Rose and A. J. Orr-Ewing, Phys. Chem. Chem. Phys., 2007, 9, 3261
    DOI: 10.1039/B704463A

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