Chen Zhen, Chen Jun, Chen Rongjun, Xie Ting, Wang Xingan, Liu Shu, Wu Guorong, Dai Dongxu, Yang Xueming, Zhang Dong H
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 116023 Dalian, China.
University of Chinese Academy of Sciences, 100049 Beijing, China.
Proc Natl Acad Sci U S A. 2020 Apr 28;117(17):9202-9207. doi: 10.1073/pnas.1917618117. Epub 2020 Apr 10.
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 → HCl + CH reaction. A distinctive peak at a collision energy of 0.15 eV for the CH( = 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.
长期以来,人们一直预测,在重-轻-重(HLH)化学反应中,作为碰撞能量的函数,反应性存在振荡行为,其中轻原子在两个重原子或原子团之间转移,但在双分子反应中直接观察到这种行为仍然是一个挑战。在此,我们报告了一项关于Cl + CH → HCl + CH反应的联合理论和交叉分子束研究。在向后散射方向上,实验检测到CH( = 0)产物在碰撞能量为0.15 eV时出现一个独特的峰。在高精度势能面上进行的详细量子动力学计算表明,这一特征源于该HLH多原子反应中的反应性振荡。我们预计,这种反应性振荡存在于许多涉及多原子试剂的HLH反应中。