Collisional dissociation of dimers by monomers in rare gases

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Abstract
Cross sections and thermal rate coefficients for single‐collision dissociation in ground‐state Rg2 by Rg (Rg = Ne,Ar,Kr, and Xe) were computed using Monte Carlo quasiclassical trajectories. The influence of vibrational and rotational excitation of the dissociation cross sections and rate coefficients was investigated for Ar+Ar2. The following conclusions are reached. At high collision energies the cross section for dissociation of ground‐state dimers is given by πR2e (where Re is the equilibrium internuclear separation of the dimer). Initial vibrational excitation greatly enhances dissociation; initial rotation also enhances dissociation but not to the extent that vibration does. The temperature dependence of the rate coefficients for dissociation of ground‐state dimers is shown to be well described by k = CT−1/3. The rate of Ar2 dissociation by Ar is found to be orders of magnitude greater than previously reported values.