KINETIC-ENERGY RELEASE IN UNIMOLECULAR DECOMPOSITIONS OF IONS - HYPROGEN REARRANGEMENTS

The partition of reverse activation energy in hydrogen rearrangements is considered in terms of atomic motions composing the transition state reaction coordinate. It is shown how this approach predicts that, in general, elimination of H2 from any small ion (as defined in the paper) is likely to be characterized by partition of significant proportions of any reverse activation energy as translational energy of the products. Hydrogen rearrangements in large ions leading to fragments of comparable mass are much less likely to partition reverse activation energy into product translation. Copyright © 1979 John Wiley & Sons, Ltd.