Initial state effects in the vibrational predissociation of hydrogen fluoride dimer

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Abstract
The state‐to‐state vibrational predissociation dynamics of the hydrogen fluoride dimer has been investigated in detail using a newly developed instrument which gives both initial state selection and photofragment state determination. Results are reported for a wide variety of initial states associated with the ν1 and ν2 vibrations. The final state distributions universally indicate that the preferred dissociation channels correspond to the production of one HF fragment that is highly rotationally excited and another that is not. This is explained in terms of an impulsive dissociation mechanism which proceeds from a geometry close to that of the equilibrium structure of the dimer. We find that nearly degenerate initial states can have rather different final state distributions. In particular, there is a distinct difference between the upper and lower members of the tunneling doublet, which is most likely attributable to their related symmetries. The dissociation energy (D0) is determined to be 1062±1 cm−1.