Nitromethane - Methyl Nitrite Rearrangement: The Seising of Discrepancy between Theory and Experiment

The potential energy hyper surfaces (FES) of the unimolecular rearrangements of a) Nitromethane itei totrans acknitromethane b) nitrometharie (/) to methyl nitrite (3) and c) naromethane decomposition tomethyl and nitrogen dioxide were searched using the ab !nth° MP2 method. Split valence 6-310(d.p) basisset was used for geometry optimizations, frequency and 1RC computations along each reaction pan. Theenergy barrier for the decomposition path or nitremethane was found to be 87.8 kcal/mot net newlydetermined transition state. The nitromeihane to methyl nitrite bent bight was previously determined tohe the 70.5 kealimol. which is 17.3 kcal/mol less than nat of the nitromethane decomposition path repottedin WE won. Using these data it was possible for the first time to explain the experimentally observed pathof nitromethane decomposition