The mass spectrum of nitromethane points to rupture of the CH 3 NO 2 bond as the dominant primary reaction, as also observed in pyrolysis, photolysis and radiolysis. Isomerization of the molecular ion to the nitrite configuration seems to contribute little in the mass spectrum of nitromethane, in contrast to those of nitrobenzene and other nitroarenes. The nitrite ion is probably the immediate precursor of [NO] + at its appearance potential, but most of the [NO]+ yield seems to stem from secondary decomposition of excited [NO 2 ] + .
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Meyerson et al. (1974) studied this question.
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