DENSITY FUNCTIONAL THEORY STUDY ON THE DECOMPOSITION MECHANISMS OF POLYNITROTRIPRISMANES: C6H6-n (NO2)n (n = 2, 4, 6)

Abstract

Density functional theory (DFT) has been carried out to predict some possible decomposition pathways of polynitrotriprismanes C 6 H 6-n ( NO 2)n (n = 2, 4, 6) at B3LYP/6-31 + G (d, p) level. The calculated results (BDE298) suggest that the most preferred dissociation reaction for these compounds involves an initial rupture of C–C bond in the triprismane cage skeleton, followed by an opening of the second C–C bond of the intermediate to form nitro Dewar benzene, which has a similar reaction pathway as that of octanitrocubane. In addition, the predicted reaction energy shows that the whole decomposition reaction is exothermic, and the rupture of the second C–C bond is mainly the energy origin of these compounds. The predicted dissociation route for three selected PNNPs will be very helpful not only for synthesis of PNNPs, but also for characterization of other nitro-substituted high energy density materials (HEDMs).