A classical trajectory study of the effect of reaction barrier height on the vibrational energy transfer efficiency in the Cl + HCl system

✍ Scribed by Ronald L. Thommarson; George C. Berend

• Publisher: John Wiley and Sons
• Year: 1973
• Tongue: English
• Weight: 637 KB
• Volume: 5
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550050413

✦ Synopsis

Abstract

The effects of reaction barrier height and initial rotational excitation of the reactants on the overall rate of H atom exchange between atomic chlorine and HCl (v = 0) and on the 0 → 1 vibrational excitation of HCl via reactive and nonreactive collisions have been investigated using quasiclassical trajectory techniques. Two empirical LEPS potential energy surfaces were employed in the calculations having reaction barrier heights of 9.84 and 7.05 kcal mol^−1^. Trajectory studies of planar collisions were carried out on each surface over a range of relative translational energies with the ground‐state HCI collision partner given initial rotational excitation corresponding J = 0, 3, and 7. Initial molecular rotation was found to be relatively inefficient in promoting the H atom exchange; the computed rate coefficient for H atom exchange between Cl + HCl (v = 0, J = 7) was only 4 times larger than that for CI + HCI (v = 0, J = 0). The vibrational excitation rate coefficient exhibited a stronger dependence on initial molecular rotational excitation. The observed increase in the vibrational excitation rate coefficient with increasing initial molecular rotational excitation was due primarily to nonreactive intermolecular R → V energy transfer. The vibrational excitation rate coefficients increase with decreasing reaction barrier height.