KrF Laser Induced Decomposition of Tetranitromethane

Electronic excitation of tetranitromethane (TNM) in aerated or deaerated polar solvents generates the NO2 radical and the nitroform anion, (N02)3C-, which has a maximum absorption at 350 nm. In nonpolar solvents electronic excitation of TNM leads to the formation of the NO2 radical and the trinitromethyl radical, (NO2)3C·, with an absorption maximum at 307 nm. Prolonged irradiation of TNM in nonpolar solvents results in the formation of nitroform, (NO2)3C-H which is probably generated by the (NO2)3C· via hydrogen abstraction from the solvent. The nonpolar solvent radicals generated by the hydrogen abstraction reaction combine with NO2 radicals in the solution to form nitroalkane molecules.