Ab initio calculations of reactive pathways for ?-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (?-HMX)

abstractUsing the BLYP and B3LYP level of density functional theory, four possible decomposition reaction pathways of HMX in the gas phase were investigated: N?NO2 bond dissociation, HONO elimination, C?N bond scission of the ring, and the concerted ring fission. The energetics of each of these four mechanisms are reported. Dissociation of the N?NO2 bond is putatively the initial mechanism of nitramine decomposition in the gas phase. Our results find the dissociation energy of this mechanism to be 41.8 kcal/mol at the BLYP level and 40.5 kcal/mol at the B3LYP level, which is comparable to experimental results. Three other mechanisms are calculated and found at the BLYP level to be energetically competitive to the nitrogen?nitrogen bond dissociation; however, at the B3LYP level these three other mechanisms are energetically less favorable. It is proposed that the HONO elimination and C?N bond scission reaction of the ring would be favorable in the condensed phase