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G3(MP2) Study of the C3H6O+• Isomers Fragmented from 1,4-Dioxane+•

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journal contribution
posted on 18.08.2005, 00:00 authored by Chow-Shing Lam, Wai-Kee Li, See-Wing Chiu
The fragmentation process of ionized 1,4-dioxane and the reactions between the C3H6O+• ions, one of the major fragments, and various reactants (including acetonitrile, formaldehyde, ethylene, and propene) have been studied experimentally with mass spectrometry. In the present work, G3(MP2) calculations were carried out to investigate these processes theoretically. In agreement with experiment, isomers CH3OCHCH2+• (1) and CH2CH2OCH2+ (2) were found to be the C3H6O+• ions fragmented from ionized 1,4-dioxane, with 2 being the major product. The mechanisms of the formation of 1 and 2 were successfully established. In addition, the characteristic reactivities, as well as the corresponding reaction mechanisms, of both isomers were rationalized with the aid of calculations. Finally, a minor reaction between isomer 2 and propene was identified, and the presence of the product of this reaction was found to be useful in explaining the aforementioned mass spectrometric data.