Temperature dependence of reactions involving electron transfer in K(np)/C2Cl4 collisions

Abstract

Electron transfer in K(np)-C(2)Cl(4) collisions, which leads to formation of both Cl(-) and C(2)Cl(4)(-) anions, is investigated as a function of target temperature over the range of 300-650 K. Measurements at high n (n approximately 30) show that the likelihood of Cl(-) production increases rapidly with temperature indicating the presence of a dissociation barrier. The data yield an activation energy of approximately 0.1 eV. A broad distribution of product C(2)Cl(4)(-) lifetimes is observed that extends from microseconds to milliseconds, this distribution moving toward shorter lifetimes as the target temperature is increased. The measured lifetimes are consistent with the predictions of quasiequilibrium theory. Studies at low n (n approximately 14) show a substantial fraction of the product K(+)-Cl(-) and K(+)-C(2)Cl(4)(-) ion pairs is electrostatically bound leading to creation of heavy-Rydberg ion-pair states. Variations in target temperature lead to changes in kinetic energy of relative motion of the reactants that can result in marked changes in the fraction of ion pairs that is bound, especially at low Rydberg atom velocities. In the case of bound K(+)-C(2)Cl(4)(-) ion pairs a few percent subsequently dissociate by the conversion of internal energy in the anion into translational energy of the ion pair. Analysis of the data points to a mean energy conversion of approximately 60-90 meV, much less than the available excess energy of reaction, approximately 0.7 eV.