Dinitrites are effective nitrosating reagents in preparative chemistry and their decomposition products are involved in the atmospheric reaction of volatile organic compounds with nitrogen oxides (NO). In this work, photodissociation dynamics of five alkyl dinitrites were investigated by detecting the LIF spectra of the dissociation products and theoretical calculations. The results showed that the C-C bond connecting the two nitrosooxy (-ONO) functional groups was the weakest bond in vicinal dinitrites and aldehydes were the dissociation products. For dinitrites with two ONO groups separated by a CH group, vinoxy and 1-methylvinoxy radicals were detected as the fragments via photodissociation, indicating a different mechanism compared to thermal decomposition. This observation demonstrated that a new reactive pathway could be initiated by photolysis of dinitrites.
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