DECOMPOSITIONS OF THE METASTABLE [CH2C(OH)2]+-ION - TEST OF THE APPLICABILITY OF THE ENERGY RANDOMIZATION HYPOTHESIS TO UNIMOLECULAR FRAGMENTATIONS

The energy randomization postulate of the quasi-equilibrium theory of mass spectrometry is tested by comparing the decomposition patterns of metastable [CH2C(OH)(OD)]+· ions generated so that the origins of OH and OD were interchanged. The [CH2C(OH)2]+· ion either loses water directly, or it rearranges to the acetic acid ion and loses OH or CH3. Metastable [CH2C(OH)(OD)]+· ions gave the same decomposition patterns, independently of whether the OH or the OD was formed by rearrangement. This is consistent with randomization of the internal energy of the decomposing ions being complete in the 10-6-10-5 s that preceded the studied decompositions. © 1979 American Chemical Society.