Zhang Dong, Yang Jiayue, Chen Zhen, Chen Rongjun, Jiang Bo, Dai Dongxu, Wu Guorong, Zhang Donghui, Yang Xueming
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China.
Phys Chem Chem Phys. 2017 May 24;19(20):13070-13074. doi: 10.1039/c7cp01428g.
The effects of CH stretching excitation on the reactivity of the F + CHD → HF + CD reaction were studied experimentally using crossed-beam and time-sliced velocity map imaging techniques over the collision energy range of 1.21 to 9.00 kcal mol. The experimental results showed that the CH stretching excitation promoted its cleavage and enhanced the title reaction at low collision energies. This enhancement dropped with an increase of the collision energy. And at high collision energies, CH stretching excitation appeared to lower the reactivity of the above reaction, in contrast to the case at low collision energies. This decreasing trend in the enhancement of reactivity was in agreement with previous theoretical studies. The vibrationally excited reaction was further compared with the ground-state reaction at a same total reagent energy of 9.80 kcal mol, and similar reactivities were derived.
利用交叉分子束和时间切片速度成像技术，在1.21至9.00 kcal mol的碰撞能量范围内，对CH伸缩振动激发对F + CHD → HF + CD反应活性的影响进行了实验研究。实验结果表明，在低碰撞能量下，CH伸缩振动激发促进了其裂解并增强了上述反应。随着碰撞能量的增加，这种增强作用下降。在高碰撞能量下，与低碰撞能量的情况相反，CH伸缩振动激发似乎降低了上述反应的活性。反应活性增强的这种下降趋势与先前的理论研究一致。在相同的总反应物能量9.80 kcal mol下，进一步将振动激发反应与基态反应进行了比较，得到了相似的反应活性。
