Theoretical and Experimental Analysis of Ammonia Ionic Clusters Produced by 252Cf Fragment Impact on an NH3 Ice Target

Abstract

Positive and negatively charged ammonia clusters produced by the impact of (252)Cf fission fragments (FF) on an NH(3) ice target have been examined theoretical and experimentally. The ammonia clusters generated by (252)Cf FF show an exponential dependence of the cluster population on its mass, and the desorption yields for the positive (NH(3))(n)NH(4)(+) clusters are 1 order of magnitude higher than those for the negative (NH(3))(n)NH(2)(-) clusters. The experimental population analysis of (NH(3))(n)NH(4)(+) (n = 0-18) and (NH(3))(n)NH(2)(-) (n = 0-8) cluster series show a special stability at n = 4 and 16 and n = 2, 4, and 6, respectively. DFT/B3LYP calculations of the (NH(3))(0)(-)(8)NH(4)(+) clusters show that the structures of the more stable conformers follow a clear pattern: each additional NH(3) group makes a new hydrogen bond with one of the hydrogen atoms of an NH(3) unit already bound to the NH(4)(+) core. For the (NH(3))(0)(-)(8)NH(2)(-) clusters, the DFT/B3LYP calculations show that, within the calculation error, the more stable conformers follow a clear pattern for n = 1-6: each additional NH(3) group makes a new hydrogen bond to the NH(2)(-) core. For n = 7 and 8, the additional NH(3) groups bind to other NH(3) groups, probably because of the saturation of the NH(2)(-) core. Similar results were obtained at the MP2 level of calculation. A stability analysis was performed using the commonly defined stability function E(n)(-)(1) + E(n)(+1) - 2E(n), where E is the total energy of the cluster, including the zero point correction energy (E = E(t) + ZPE). The trend on the relative stability of the clusters presents an excellent agreement with the distribution of experimental cluster abundances. Moreover, the stability analysis predicts that the (NH(3))(4)NH(4)(+) and the even negative clusters [(NH(3))(n)NH(2)(-), n = 2, 4, and 6] should be the most stable ones, in perfect agreement with the experimental results.