Liu Shu, Zhang Xiaoren, Chen Jun, Zhang Dong H
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
University of Chinese Academy of Sciences, Beijing 100049, China.
J Phys Chem Lett. 2021 Jul 8;12(26):6090-6094. doi: 10.1021/acs.jpclett.1c01586. Epub 2021 Jun 25.
Experiments and theories showed the ground-state reaction F + HO → HF + OH possesses Feshbach resonances trapped in the hydrogen bond well in the product region. However, it is not clear whether F + HO and its isotopic analogues have the same Feshbach resonances caused by chemical bond softening as those in the F + H/HD. Here, we reported state-to-state quantum dynamics studies of the F + HOD( = 1) → HF + OD and F + HOD( = 1) → DF + OH reactions on an accurate neural network potential energy surface. Detailed analysis reveals that the course of the title reactions is dominated by the Feshbach resonance states trapped in the peculiar HF('=3)-OD/DF('=4)-OH vibrationally adiabatic potential well created by the HF/DF bond softening, which can only be accessed via the HOD( = 1)/HOD( = 1) reaction pathway. Therefore, we confirm the wide existence of chemical bond softening resonances in reactions involving vibrationally excited molecules.
实验和理论表明，基态反应F + HO → HF + OH在产物区域的氢键阱中存在费什巴赫共振。然而，尚不清楚F + HO及其同位素类似物是否具有与F + H/HD中由化学键软化引起的相同费什巴赫共振。在此，我们报道了在精确的神经网络势能面上对F + HOD( = 1) → HF + OD和F + HOD( = 1) → DF + OH反应的态-态量子动力学研究。详细分析表明，标题反应的过程由被困在由HF/DF键软化产生的特殊HF('=3)-OD/DF('=4)-OH振动绝热势阱中的费什巴赫共振态主导，该势阱只能通过HOD( = 1)/HOD( = 1)反应途径进入。因此，我们证实了在涉及振动激发分子的反应中化学键软化共振的广泛存在。
