Abstract
The loss of alkane molecules from metastable aliphatic alcohol and ether radical cations in the gas phase can be used to probe the properties of intermediate weakly bonded ion-neutral complexes. Very little translational energy is released when the final products form a stable complex prior to dissociation, whereas the energy released can directly reflect the heat of reaction when dissociation takes place subsequent to an exothermic intra-complex reaction. The heats of formation of the intermediate oxonium ions and the product radical cations of enols and enol ethers were determined using the composite G2(MP2) and CBS-Q high-level ab initio methods.
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