Trajectory study of the effect of energy barrier location on the energy disposal for the reaction O(3P) + Cl2 → OCl + Cl

Abstract

The mode of partitioning of total energy available in the reaction O(3P) + Cl2 → OCl + Cl is investigated as a function of the initial collision energy, in correlation with Polanyi's adiabaticity rules, using a series of related LEPS-type potential energy functions. All surfaces possess a classical energy barrier of similar height located in the entrance valley of the reaction, but present a small, gradual displacement of the top of the barrier to later positions along the approach coordinate. Quasiclassical trajectory calculations on these surfaces indicate marked differences in the disposal of total energy and the dynamical behaviour of the reaction. Also the effect of excess reagent vibration is investigated.