Theoretical study of the competition between various mechanisms of gas-phase decomposition in the series of primary N-nitramines

Nonempirical and density-functional methods were used to determine geometric parameters, enthalpies of formation of compounds and radicals, dissociation energies of the N-NO₂ bonds of primary N-nitramines and N,N-dinitramines. The tendencies toward variation of the geometric structure, enthalpies of formation, and dissociation energy in the series of primary N-nitramines were analyzed. Alternative mechanisms of the gas-phase thermal destruction to give experimentally observed reaction products were studied for the example of N-methylnitramine and its homologues.