Energetic Metastable Decompositions
- 15 November 1969
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 51 (10), 4633-4642
- https://doi.org/10.1063/1.1671836
Abstract
A study of the shape of metastable peaks observed in a mass spectrometer was carried out. The shape of the peak is related to the distribution of kinetic energies released in the decomposition. For Gaussian-shaped metastable peaks the kinetic-energy distribution is approximately Boltzmann, while for flat-topped metastable peaks the energy distribution is reversed, with the most probable energy greater than the average energy released. The 31+ − 29+ transition which is accompanied by a flat-topped metastable peak was examined in detail. Molecular-orbital calculations reveal that the reaction may involve tunneling through a barrier formed by the crossing of an attractive and repulsive state. The transition state is examined in detail and compared to the semi-ion pair model for a four-center elimination reaction.Keywords
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