Publication Date:
2014-08-19
Description:
By exciting the rotational modes of vibrationally excited CHD 3 ( v 1 = 1, JK ), the reactivity for the Cl + CHD 3 → HCl + CD 3 reaction is observed enhanced by as much as a factor of two relative to the rotationless reactant. To understand the mode specificity, the reaction dynamics was studied using both a reduced-dimensional quantum dynamical model and the conventional quasi-classical trajectory method, both of which reproduced qualitatively the measured enhancements. The mechanism of enhancement was analyzed using a Franck-Condon model and by inspecting trajectories. It is shown that the higher reactivity for higher J states of CHD 3 with K = 0 can be attributed to the enlargement of the cone of acceptance. On the other hand, the less pronounced enhancement for the higher J = K states is apparently due to the fact that the rotation along the C–H bond is less effective in opening up the cone of acceptance.
Print ISSN:
0021-9606
Electronic ISSN:
1089-7690
Topics:
Chemistry and Pharmacology
,
Physics
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