Journal of Chemical Physics, Vol.106, No.6, 2265-2276, 1997
Translational to Vibrational and Rotational (T-)V,R) Energy-Transfer and Reactive Exchange Collisions of H(D)+hf(DF) in the Energy-Range from 1 to 2 eV by Time-Resolved Fourier-Transform Spectroscopy
The product state distributions for hot atom collisions of H(D) with HF(DF) with a broad range of collision energies between 1.2 eV and 2.3 eV are measured with time-resolved Fourier transform spectroscopy and rotational resolution under multiple collision conditions. In most cases the vibrational distributions of reactive and nonreactive channels can be distinguished, All rotational distributions have a similar appearance with a maximum at J=5 and an additional pronounced higher component, which cannot be described by a single Boltzmann distribution. The results are compared with recent three dimensional quasiclassical trajectory calculations (accompanying paper by Schatz) by applying a multiple collision model for both the H(D) atom slowdown and the rotational and vibrational relaxation. The rotational distributions can also be interpreted by a three dimensional asymmetric breathing ellipsoid model.
Keywords:DOUBLE-RESONANCE MEASUREMENTS;MECHANICAL REACTION PROBABILITIES;CROSSED MOLECULAR-BEAM;F + D2;TRANSITION-STATE;F+H-2 REACTION;FTIR EMISSION;PHOTODISSOCIATION DYNAMICS;TEMPERATURE-DEPENDENCE;RATE COEFFICIENTS