Journal of Physical Chemistry A, Vol.101, No.50, 9699-9703, 1997
Reactive scattering of OD radicals with ICl and Br-2 molecules at initial translational energy E similar to 90kJmol(-1)
Reactive scattering of OD radicals with ICl and Br-2 molecules has been studied at an initial translational energy E similar to 90 kJ mol(-1) using a supersonic beam of OD radicals seeded in He buffer gas generated from a high-temperature radio frequency discharge source. The center-of-mass angular distribution of DOI scattering from OD + ICl shows sharp forward and backward peaking with the relative intensity of the backward peak being lower by a factor similar to 0.6 +/- 0.1. The DOBr scattering from OD + Br-2 shows broader peaking in the forward direction declining to a lower intensity similar to 0.8 +/- 0.2 in the backward direction. In both cases the product translational energy distributions peak at low energy with a tail extending out to higher energy. Comparison with the predictions of phase space theory indicates that the OD + ICl reaction proceeds via a DOICl collision complex with a lifetime of approximately one rotational period, while the OD + Br-2 reaction shows evidence for the migration of the OD radical between the Br atoms of a DOBrBr complex. The DOICl complex corresponds to a significant well of depth E-0 similar to 80 kJ mol(-1) on the potential energy surface for the OD + ICl reaction while the potential energy surface for the OD + Br-2 reaction also supports a shallow minimum.