Vibrational versus translational energies in the H + CCl 4 reaction: A quasi-classical trajectory study

Abstract

The effects of vibrational versus translational energies in the dynamics of the light–heavy–heavy H + CCl 4 reaction were examined by performing trajectory calculations on an analytical surface developed by our group. For this ‘early transition state’ reaction, translational energy was found to be considerably more effective at driving the reaction than an equivalent amount of vibrational energy, thus extending the validity of Polanyi rules to this polyatomic system. This behaviour was explained on the basis of there being little or negligible intramolecular vibrational redistribution in the CCl 4 reactant before collision with the H atom.