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- Title
Revealing the stereospecific chemistry of the reaction of Cl with aligned CHD<sub>3</sub>(?<sub>1</sub> = 1).
- Authors
Wang, Fengyan; Liu, Kopin; Rakitzis, T. Peter
- Abstract
The concept of geometrical constraints and steric hindrance in reactions is implanted deeply in a chemist's 'chemical intuition'. However, until now a true three-dimensional view of these steric effects has not been realized experimentally for any chemical reaction in full. Here we report the complete three-dimensional characterization of the sterics of a benchmark polyatomic reaction by measuring the dependence of the product state-resolved angular distributions on the spatial alignment of the reactive bond in a crossed molecular beam experiment. The results prove the existence of two distinct microscopic reaction mechanisms. Detailed analysis reveals that the origin of the stereodynamics in the HCl(? = 0) + CD3(00) product channel can be captured by a textbook line-of-centres collision model. In contrast, a time-delay pathway, which includes a sharp switch from in-plane to out-of-plane scattering in the forwards direction, appears to be operative in forming the excited HCl(? = 1) + CD3(00) product pair.
- Subjects
CHEMICAL reactions; CHLORINE; MOLECULAR beams; REACTION mechanisms (Chemistry); POLYATOMIC molecules
- Publication
Nature Chemistry, 2012, Vol 4, Issue 8, p636
- ISSN
1755-4330
- Publication type
Article
- DOI
10.1038/nchem.1383