The vibration and decomposition of the hydrogen peroxide molecule

. A complete vibrational analysis is worked out for hydrogen peroxide, using the data of Giguere & Bain. The FG matrix method of Howard & Wilson is employed, use being made of symmetry co-ordinates. The amplitude factors corresponding to each of the six normal modes of vibration are calculated. Slater’s equation for the rate of energization of a molecule within which there can be no flow of energy between the normal modes is then employed to calculate rates, different choices of the critical reaction co-ordinate being made. The choice of the O— O distance as the critical co-ordinate leads to a rate of energization that is about 10-5 of the experimental value. The maximum possible rate predicted by the Slater equation is about 10-2 of the experimental value. The implications of these results are briefly discussed in terms of the hypothesis that there is a flow of energy between the normal modes of the molecule, as assumed in the treatments of Hinshelwood, Kassel, and Rice & Ramsperger.