Computational studies on polynitrohexaazaadmantanes as potential high energy density materials.

Polynitrohexaazaadamantanes (PNHAAs) have been the subject of much recent research because of their potential as high energy density materials (HEDMs). The B3LYP/6-31G method was employed to evaluate the heats of formation (HOFs) for PNHAAs by designing isodesmic reactions. The HOFs are found to be correlative with the number (n) and the space orientations of nitro groups. Detonation velocities (D) and detonation pressures (P) were estimated for PNHAAs by using the well-known Kamlet-Jacobs equations, based on the theoretical densities (rho) and HOFs. It is found that D and P increase as n ranges from 1 to 6, and PNHAAs with 4-6 nitro groups meet the criteria of an HEDM. When n is over 6, rho of PNHAAs slightly increases; however, the chemical energy of detonation (Q) decreases so greatly that both D and P decrease. The calculations on bond dissociation energies suggest that the N-N bond be the trigger bond during the pyrolysis initiation process of each PNHAA, and with increasing n, N-N bond dissociation energy (E(N-N)) decreases on the whole, that is to say, the relative stability of PNHAAs decreases. All E(N-N)(s) of PNHAAs are more than 30 kcal.mol(-1), which further proves that four PNHAAs with 4-6 nitro groups can be used as the candidates of HEDMs. Considering the synthesis difficulty and the performance as an energetic compound, we finally recommended 2,4,6,8,10-pentanitrohexaazaadamantane as the target HEDM for PNHAAs.