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Additional resources for Advances in Chemical Physics: Molecular Scattering: Physical and Chemical Applications, Volume 30
Fig. 8 compares experimental and theoretical product velocity distributions for Cs SF,. Phase-space and RRKM theories have also been applied t o a series of experiments designed to explore whether or not randomization in a reaction complex is fast relative to decomposition of the complex. , 1973) show qualitative agreement between experiment and RRKM predictions of branching ratios. Product energy distributions, on the other hand, do not agree. This suggests that the assumption of randomization of the complex internal energy breaks down at the transition state.
Shipsey has employed his own set of coordinates (1969,1972)in a calculation (1973)of PrJuffor 0 + HBr + OH + Br, with uf = 0,1,2. This reaction has an exoergicity of about 1 eV. 00264 eV in the entrance valley. 315 eV; the 0 2 one was not appreciable until after about 0-12eV. Good agreement was found (Koeppl, 1973) between these numerical results and absolute reaction rate theory at threshold energies. Two other attempts have been made by Crawford. In the first one (1971a) an R-matrix approach was used, following the Wigner-Eisenbud procedure.
MICHA sections, for example over a distribution of collision energies. Let us indicate the scattering channels for one rearrangement by a, for another one by b, and so on. If obU(ku) is the cross section for a -+ b reaction at collision energy E , = h2k:/(2p,), and the number of E , values within dE, is given by p(E,) d E , , which we assume is peaked at a particular k,, then This cross section may be expressed in terms of S-matrix elements, which are in turn obtained from the asymptotic form of total wavefunctions Y .