Density functional theory calculations on the thermodynamic properties of polynitrosoprismanes

A series of polynitrosoprismanes, C6H6 - n (NO) (n) (n = 1-6), considered as high energy density compounds (HEDCs), have been designed computationally. We calculated the electronic structures, the heats of formation, the specific enthalpies of combustion, the bond dissociation energies, and the strain energies of the title compounds using density functional theory (DFT) with the 6-311G** basis set. It was found that the Delta E (LUMO-HOMO) values of the title compounds decrease as the number of nitroso groups increase, and the energy gaps of the prismane derivatives are much lower than that of TATB. Their high positive heats of formation indicate that polynitrosoprismanes can store a great deal of energy. Furthermore, the HOFs for the nitrosoprismane series were observed to decrease until three nitroso groups were connected to the prismane skeleton. For the polynitrosoprismanes, the trigger bond was confirmed to be the C-C bond in the skeleton. According to our calculations, all nitrosoprismanes appear to have large strain energies, and these calculations can provide basic information that may prove useful for the molecular design of novel high energy density materials.