Comparing reactions of H and Cl with C-H stretch-excited CHD3

Jon P Camden; Hans A Bechtel; Davida J Ankeny Brown; Richard N Zare

doi:10.1063/1.2155434

Comparing reactions of H and Cl with C-H stretch-excited CHD3

J Chem Phys. 2006 Jan 21;124(3):034311. doi: 10.1063/1.2155434.

Authors

Jon P Camden¹, Hans A Bechtel, Davida J Ankeny Brown, Richard N Zare

Affiliation

¹ Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA.

PMID: 16438587
DOI: 10.1063/1.2155434

Abstract

We report the methyl radical product state distributions for the reactions of H and Cl with CHD3(nu1 = 1,2) at collision energies of 1.53 and 0.18 eV, respectively. Both reactions demonstrate mode selectivity. The resulting state distributions from the H+CHD3(nu1 = 1,2) reactions are well described by a spectator model. The reactions Cl + CHD3(nu1 = 1,2) exhibit similar behavior, but in some aspects the spectator model breaks down. We attribute this breakdown to enhanced intramolecular vibrational redistribution in the Cl + CHD3(nu1 = 1,2) reactions compared to the H + CHD3(nu1 = 1,2) reactions, caused by the interaction of the slower Cl atom with the vibrationally excited CHD3, which is promoted either by its longer collision duration, its stronger coupling, or both.