Dynamics of heavy + light–heavy atom transfer reactions. The reaction Cl + HCl → ClH + Cl

Abstract

The effect of reactant rotational energy on the dynamics of the light-atom-transfer reaction Cl + HCl(v= 0, j)→ ClH + Cl has been investigated on an extended London–Eyring–Polanyi–Sato (LEPS) potential-energy surface using the centrifugal-sudden distorted-wave (CSDW) method, together with quasiclassical trajectory (QCT) computations. CSDW cross-sections have been calculated at total energies of E_total= 0.40 and 0.50 eV, whilst QCT cross-sections were computed at E_total= 0.50, 0.60, 0.70 and 1.183 eV. In all cases we find that reactant rotational energy is very effective in promoting the reaction, and that the products are formed in highly excited rotational states. The properties of individual trajectories during the course of the reaction have been studied, in order to gain insight into the dynamics of the reaction. For rotationally excited reactants at E_total= 0.70 and 1.183 eV, trajectories undergoing a ‘figure-of-eight’ motion from an important part of the reaction mechanism.