Abstract
The infrared multiphoton dissociation of dimethylnitramine in the gas phase by a pulsed C 0 2 laser has been studied in order to elucidate its photochemical decomposition mechanism under collisionless conditions and provide a qualitative understanding of the consequent chemical mechanism that leads to the final products. The experimentally determined steady-state rate coefficient for the unimolecular decomposition of dimethylnitramine was found to be k(st) = IOS.S*O.'(I/MW s-I for laser intensities 2-10 MW Scavenging experiments with C12, NOCI, NO, NO2, and (CD3)2NN02 molecules have shown that the decomposition dynamics proceeds through scission of the N-N02 bond, with no evidence of the HONO elimination or the isomerization to nitrc-nitrite channel. Dimethylnitrosamine was the major final product which was mainly produced through oxidation of dimethylamino radical by dimethylnitramine.
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