title: Comparing reactions of H and Cl with C-H stretch-excited CHD3.
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.
authors.affiliation: Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA.
authors.forename: Jon P
authors.initials: JP
authors.lastname: Camden
authors.forename: Hans A
authors.initials: HA
authors.lastname: Bechtel
authors.forename: Davida J
authors.initials: DJ
authors.lastname: Ankeny Brown
authors.forename: Richard N
authors.initials: RN
authors.lastname: Zare