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