Abstract
The distribution of vibrational energy is diatomic molecules following unimolecular elimination is shown to be well represented as a distribution of maximal entropy subject to a constraint on the mean vibrational excitation. The nature of the constraint does not appear to depend on the activation process. The value of the constraint depends primarily on the height of the barrier in the elimination channel and, more weakly, on the excess energy above the barrier. A quantitative expression of these trends, in the form of a “sum rule”, provides a route for the estimation of the energy distribution in the products at different total energies. The more limited results on the energy released into the relative translation or into the organic fragment can be largely accounted for using the same constraint. Different partitionings of a given total energy among the diatomic molecule and the organic olefin (or acetylene) are shown to lead to only a moderate change in the rate of addition reactions.
Original language | English |
---|---|
Pages (from-to) | 253-268 |
Number of pages | 16 |
Journal | Chemical Physics |
Volume | 52 |
Issue number | 3 |
DOIs | |
State | Published - 1980 |