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

Abstract

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.