A simple model with three variable parameters is developed for calculating observed clustering data from a free jet expansion. One parameter, sgr;R1, can be associated with a reactive collision diameter for a monomer associating with a cluster to form a larger, excited cluster. A second parameter, sgr;R3, can be associated with a reactive collision diameter for energy transfer from the excited cluster to the surrounding gas. The third parameter,Kprime;, is a constant in a unimolecular decay rate expression for the excited cluster. The reactive cross sections that give the best fit of experimental data are given by (pgr;/4) sgr;2R1=9.90times;10minus;16cm2and (pgr;/4) sgr;2R3=5.22 times;10minus;17cm2. No value could be assigned toKprime;. Apparently the excited clusters are stabilized by energy exchange collisions in this particular flow field before there is appreciable unimolecular decay. Good fits of clustering data are obtained even though these same values are used for clusters varying in size from 6 to 26 water molecules. Since the clustering environment is radically different than in nearhyphen;equilibrium experiments, it is not clear that these numbers can be used with other types of experimental data.
展开▼