Dynamical calculations are made for the reactions Hplus;H2, Dplus;D2, Dplus;H2, and Hplus;D2, for linear activated complexes, on the basis of the hypothesis that the zerohyphen;point vibrational energy of the reactant molecule passes smoothly into zerohyphen;point energy for the stretching vibrations of all of the intermediate complexes. By considering vibrations normal to the minimal reaction path, zerohyphen;point energies are calculated at each point along the path. Profiles forPthinsp;plus;thinsp;Z, the sum of the potential and zerohyphen;point energies, show single maxima at the activated state. Dynamical calculations for linear systems show that at high impact energies additional energy is required for crossing thePthinsp;plus;thinsp;Zbarrier, arising from the centrifugal effect, but that this energy approaches zero as the impact energy is reduced towards the threshold energy. Freehyphen;energy profiles are constructed for the Hplus;H2and Dplus;D2systems; at higher temperatures these show double maxima, at each side of the potentialhyphen;energy maximum.
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