Density functional theory (DFT) computation was carried out to investigate the crystal, molecular and electronic structures of high energy crystal [2,2′-bi(1,3,4-oxadiazole)]-5,5′-dinitramide (BODN) with the pressure 0–120 GPa. The relaxed crystal structure by the GGA/PBE-TS functional matches well with the experimental data at ambient pressure condition. With the intensifying of pressure, the lattice parameters, volumes, bond lengths, H-bond energies, atomic charges, bond populations, band gaps and density of states of crystal BODN change gently. Under the pressure of 48, 104, and 107 GPa, three pressure-induced transformations occurred. The intramolecular six membered rings pose strong affect in stabilizing systems in the pressure range 0–120 GPa. Between O1 and H2 atoms, the H-bond interaction transforms into covalent interaction under the circumstance of 48 GPa. At 104 GPa, structural transformation occurs with the distortion of the intramolecular six membered ring. In addition, O1⋅⋅⋅H2 and O2⋅⋅⋅H1 have the largest H-bond energies in comparison with the others. When the pressure reaches 107 GPa, the H-bond O1⋅⋅⋅H2 is formed again with the deformation and non-coplanarity of two oxadiazoles in crystal BODN. The electrons can be moved easily based on the density of states and energy bands under high pressure. Helpful information will be conveyed by this work in the field of further analysis connected the pressure effect on molecular transformations.
