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

摘要

We report the methyl radical product state distributions for the reactions of H and Cl with CHD3(nu(1)=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(nu(1)=1,2) reactions are well described by a spectator model. The reactions Cl+CHD3(nu(1)=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(nu(1)=1,2) reactions compared to the H+CHD3(nu(1)=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. (c) 2006 American Institute of Physics.