The monomolecular mechanism of the gas‐phase thermal decomposition of primary N‐nitramines

Abstract

ABSTRACT:Using nonempirical methods and DFT-methods the geometrical parameters formation enthalpies of molecules and radicals, energies dissociation of NONO 2 bonds 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 multistage destruction is the most advantageous way of decomposition of the primary N-nitramines.

New Mechanistic Insights into the Primary Thermolysis Reactions of 1,3,4,6-Tetranitrooctahydroimidazo-[4,5-d]imidazole (BCHMX) from Predictive Local Coupled Cluster Calculations

“…Initially we considered the radical N–NO 2 bond scission, , which leads to the formation of the radicals · x R1 and ·NO 2 . Among the various conformers of 1 , the reaction yielding · 1c R1 and ·NO 2 dominates the PES regions related to the radical decomposition of BCHMX, with a relative reaction enthalpy (w.r.t.…”