西亚试剂：Dynamical Resonances Accessible Only by Reagent Vibrational

Dynamical Resonances Accessible Only by Reagent Vibrational Excitation in the F + HD→HF + D Reaction

Tao Wang1，*， Jun Chen1，*， Tiangang Yang1， Chunlei Xiao1， Zhigang Sun1， Long Huang1， Dongxu Dai1， Xueming Yang1，2， Dong H. Zhang1，2

Experimental limitations in vibrational excitation efficiency have previously hindered investigation of how vibrational energy might mediate the role of dynamical resonances in bimolecular reactions. Here， we report on a high-resolution crossed-molecular-beam experiment on the vibrationally excited HD(v = 1) + F → HF + D reaction， in which two broad peaks for backward-scattered HF(v′ = 2 and 3) products clearly emerge at collision energies of 0.21 kilocalories per mole (kcal/mol) and 0.62 kcal/mol from differential cross sections measured over a range of energies. We attribute these features to excited Feshbach resonances trapped in the peculiar HF(v′ = 4)–D vibrationally adiabatic potential in the postbarrier region. Quantum dynamics calculations on a highly accurate potential energy surface show that these resonance states correlate to the HD(v′ = 1) state in the entrance channel and therefore can only be accessed by the vibrationally excited HD reagent

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