Abstract
The DC slice imaging method is used to record energy- and angle-resolved distributions for both ground-state Cl (P-2(3/2)) and spin-orbit excited Cl* (P-2(1/2)) photofragments produced from the (A) over tilde -band photolysis of CH3Cl at 193.3 nm. The dissociation is found to be highly impulsive, with similar to90% of the available energy being released into translation. The angular distributions are predominantly perpendicular in the case of both the ground state and spin-orbit excited chlorine atom fragments, as characterized by recoil-energy averaged values of beta = -0.46 and beta* = -0.74 respectively, although we find considerable variation in both channels as a function of CH3 internal energy. In contradiction with previous measurements, we conclude that the transition to the (1)Q(1) state dominates much of the (A) over tilde -band profile, and this has significant implications for the description of the dissociation dynamics. Our findings are rationalized in terms of similar measurements performed with other methyl halides and their H atom substituted analogues.
Original language | English |
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Pages (from-to) | 8106-8114 |
Number of pages | 9 |
Journal | The Journal of Physical Chemistry A |
Volume | 108 |
Issue number | 39 |
DOIs | |
Publication status | Published - 30 Sept 2004 |