Ab Initio Study of Unimolecular Decomposition of Nitroethylene

Four distinct pathways of unimolecular decomposition of nitroethylene, the C−NO 2 bond breaking, nitro-to-nitrite rearrangement, 1,2-elimination reaction and 1,1-elimination reaction, have been computationally investigated with ab initio, MP2, MP4, and G2 methods as well as with DFT methods. The nitro-to-nitrite rearrangement and 1,2-elimination reaction are found to give the lowest energy decomposition pathways for this molecule, about 15 kcal/mol lower than the cleavage of the nitro group.