Energy of the N-NO_2 bond dissociation and the mechanism of the gas-phase monomolecular thermal decomposition of aliphatic N-nitramines

摘要

Using non-empirical methods and DFT-methods the geometrical parameters formation enthalpies of molecules and radicals, energies dissociation of N-NO_2 bounds of primary and secondary N-nitramines have been investigated. The basic tendencies in the changes of the geometrical and electronic structures, formation enthalpies and dissociation energies have been analyzed in basic homologous series of nitramines. Various alternative mechanisms of the gas-phase monomolecular thermal decomposition have been studied by of the example of N-methylnitramine. The process of the aci-form formation and its further multi-stage destruction is the most advantageous way of decomposition of the primary N-nitramines.