Density functional theory (DFT) calculations were performed for a series of polynitrobenzene derivatives Some nitrobenzenes with amino groups attached were also investigated as a bench mark or as a precursor Heats of formation (HOF) were evaluated The Node, mic reactions used for the prediction of HOFs are of permutation type in terms of the substituents The HOFs increase non additively with increasing number of nitro groups The attachment of the amino groups to polynitrobenzenes dramatically decrease the HOF The HOF of hexamtrobenzene (HNB) is 344 05 kJ mol(-1) at the B3LYP/6 311 + G** level This value is much larger than that of the widely used 1,35 triamino 2 4,6 trinitrobenzene (TATB), which engenders HNB a large chemical energy of detonation The strengths of the group interactions were analyzed according to the disproportionation energy The nearest neighbor interactions in polynitrobenzenes are in the range of 27 20-55 90 kJ mol(-1) The energy barrier for the internal rotation of nitro group in nitrobenzene is 24 6 kJ mol(-1) However, the energy barrier for the internal rotation of 2 position nitro group of 1 2 3 trinitrobenzene is as large as 216 3 kJ mol(-1) The chemical energies of detonation for polynitrobenzenes with three or more nitro groups are over 6000 J g(-1) Pentamtroaniline and HNB have good performances in terms of detonation velocity and pressure