Steric Control of the Reaction of CH Stretch–Excited CHD 3 with Chlorine Atom
Authors:
- 18 February 2011
- journal article
- other
- Published by American Association for the Advancement of Science (AAAS) in Science
- Vol. 331 (6019) , 900-903
Abstract
Exciting the CH-stretching mode of CHD3 (where D is deuterium) is known to promote the C-H bond’s reactivity toward chlorine (Cl) atom. Conventional wisdom ascribes the vibrational-rate enhancement to a widening of the cone of acceptance (i.e., the collective Cl approach trajectories that lead to reaction). A previous study of this reaction indicated an intriguing alignment effect by infrared laser–excited reagents, which on intuitive grounds is not fully compatible with the above interpretation. We report here an in-depth experimental study of reagent alignment effects in this reaction. Pronounced impacts are evident not only in total reactivity but also in product state and angular distributions. By contrasting the data with previously reported stereodynamics in reactions of unpolarized, excited CHD3 with fluorine (F) and O(3P), we elucidate the decisive role of long-range anisotropic interactions in steric control of this chemical reaction.Keywords
Funding Information
- Air Force Office of Scientific Research (AOARD-10-4034)
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