Semiclassical model for analysis of dissociative electron transfer reactions involving Rydberg atoms

Abstract

Collisions between atoms in high Rydberg states and molecules that dissociatively attach free low-energy electrons can lead to ionization through capture of the excited electron by the target molecule. A Monte Carlo code is described that models the detailed kinematics of such dissociative electron transfer reactions. The model takes into account the velocity distributions of the reactants, the lifetime and decay energetics of the transient intermediate negative ion, and the electrostatic interaction between the product positive and negative ions. Data for CF3I are presented that illustrate how detailed comparisons between model predictions and experimental data can lead to a better understanding of the dynamics of dissociative electron attachment reactions. In particular, such comparisons can provide estimates of the lifetime of the intermediate negative ions and show how the excess energy of reaction is partitioned between translational and internal degrees of freedom in the dissociation process.