Real - time dynamics of clusters . III . I , Ne , ( n = 2 - 4 ) , picosecond fragmentation , and evaporation

In this paper (III) we report real-time studies of the picosecond dynamics of iodine in Ne clusters IzNe,( Iz = 2-4) + IT + nNe. The results are discussed in relation to vibrational predissociation (VP), basic to the 1,X systems, and to the onset of intramolecular vibrational-energy redistribution (IVR). The latter process, which is a precursor for the evaporation of the host atoms or for further fragmentation, is found to be increasingly effective as the cluster size increases; low-energy van der Waals modes act as the accepting (bath) modes. The reaction dynamics for I,Ne, are examined and quantitatively compared to a simple model which describes the dynamics as consecutive bond breaking. On this basis, it is concluded that the onset of energy redistribution is observed in 12Ne2. Comparison of 1,Ne and I,Ne2 to larger clusters (n=3,4) is accomplished by introducing an overall effective reaction rate. From measurements of the rates and their dependence on uf, the initial quantum number of the I3 stretch, we are able to examine the dynamics of direct fragmentation and evaporation, and compare with theory.