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Imaging Nucleophilic Substitution Dynamics

Science  11 Jan 2008:
Vol. 319, Issue 5860, pp. 183-186
DOI: 10.1126/science.1150238

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Abstract

Anion-molecule nucleophilic substitution (SN2) reactions are known for their rich reaction dynamics, caused by a complex potential energy surface with a submerged barrier and by weak coupling of the relevant rotational-vibrational quantum states. The dynamics of the SN2 reaction of Cl + CH3I were uncovered in detail by using crossed molecular beam imaging. As a function of the collision energy, the transition from a complex-mediated reaction mechanism to direct backward scattering of the I product was observed experimentally. Chemical dynamics calculations were performed that explain the observed energy transfer and reveal an indirect roundabout reaction mechanism involving CH3 rotation.

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