Reactivity oscillation in the heavy-light-heavy Cl + CH<sub>4</sub> reaction.

Chen, Zhen; Chen, Jun; Chen, Rongjun; Xie, Ting; Wang, Xingan; Liu, Shu; Wu, Guorong; Dai, Dongxu et al. · Proc Natl Acad Sci U S A · 2020

basic_science · Level V

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Abstract

It has long been predicted that oscillatory behavior exists in reactivity as a function of collision energy for heavy-light-heavy (HLH) chemical reactions in which a light atom is transferred between two heavy atoms or groups of atoms, but direct observation of such a behavior in bimolecular reactions remains a challenge. Here we report a joint theoretical and crossed-molecular-beam study on the Cl + CH<sub>4</sub> → HCl + CH<sub>3</sub> reaction. A distinctive peak at a collision energy of 0.15 eV for the CH<sub>3</sub>(<i>v</i> = 0) product was experimentally detected in the backward scattering direction. Detailed quantum-dynamics calculations on a highly accurate potential energy surface revealed that this feature originates from the reactivity oscillation in this HLH polyatomic reaction. We anticipate that such reactivity oscillations exist in many HLH reactions involving polyatomic reagents.