DFT/BLYP/DNP is employed to calculate bond dissociation energy of X-NO2 (X = C. N, O) and Mulliken charges of nitro group of 14 kinds of nitro compounds, and partial least squares approximation is applied to linearly fit their shock initiation pressure (p(90%,TMD)). It is found that the fitted values are in good agreement with the experimental shock initiation pressures. The fitted model is used to predict the shock initiation pressures of two kinds of explosives, TNB and TNETB. The predictive values are in accordance with experimental ones. It reflects that bond dissociation energy of X-NO2 (X =C, N, O) and Mulliken charge of nitro groups may be the important factors influencing the shock sensitivity of nitro compounds. On the basis of the fitted model, bond dissociation energy of X-NO2 (X = C) and Mulliken charges of nitro groups of another 14 kinds of heterocyclic nitro compounds are in consideration to predict shock sensitivity. This work is meaningful in further understanding the shock mechanism and helpful to the design and synthesis of novel energetic materials. (C) 2010 Elsevier B.V. All rights reserved.