The DFT-B3LYP method, with basis set 6-31G*, is employed to optimize molecular geometries and electronic structures of a series of nitramines and nitro arenes. The averaged molar volume (V) and theoretical density (ρ) are estimated using the Monte-Carlo method based on 0.001 e•bohr^－3 density space. Subsequently, on the basis of the theoretical density and en-thalpy of formation (ΔH_f) which is calculated by using the PM3 method, the detonation velocity (D) and pressure (p) of the explosives are estimated by using the Kamlet-Jacbos equation, and we found that the detonation characteristics of the multicyclic nitramines is superior to nitro arenes. Consequently, we ought to pay more attention to the multicyclic nitramines in seeking high energy density materials (HEDM). The reliability of this theoretical method and results are tested by comparing the theoretical values of ρ and D with the experimental or referenced values. The theoretical val-ues of D and p are compared with the experimental values of electric spark sensitivity (E_ES). It is found that, there are quantitative relationships between the experimental E_ES values and the theoretical values of D and p if the titled com-pounds are particularly classified. In addition, we have discussed that the substituting groups have effects on density, detonation velocity and pressure, and the result suggests that such a theoretical approach can be used to predict their E_ES values which are difficult to predict quantitatively or to synthesize. In addition, we discussed the effects of substituting groups on density, detonation velocity and detonation pressure, and the obtained result is advantageous to design the molecules.

Key words: a series of nitramines and nitro arenas, density functional theory, density, detonation velocity, detonation pressure, electric spark sensitivity