Quantum reaction dynamics study of vibrational excitation effects on the Cl + CHD3/CD4 → HCl/DCl + CD3 reactions

Abstract

Energy efficiency in surmounting the reaction energy barrier and vibrational enhancement on reactivity of the Cl+CHD3/CD4→HCl/DCl+CD3 reactions have been studied using the reduced dimensional, time-dependent wavepacket method in six degrees of freedom. All the vibrational excitations of CHD3/CD4 enhance the reactivity and the C–H/C–D stretching motions have the biggest impact on the reactivity. Both reactions’ vibrational energies raise the reactivity more effectively than the translational energies except at very low collision energies. In other words, except at very low collision energies, the Polanyi rules hold for these two late-barrier polyatomic reactions.