Imaging nucleophilic substitution dynamics.

Mikosch, J; Trippel, S; Eichhorn, C; Otto, R; Lourderaj, U; Zhang, J X; Hase, W L; Weidemüller, M et al. · Science · 2008

basic_science · Level V

Where this comes from

Abstract

Anion-molecule nucleophilic substitution (S(N)2) 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 S(N)2 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.