Molecular Dynamics Studies of the Structural Change in 1,3-Diamino-2,4,6-trinitrobenzene (DATB) in the Crystalline State under High Pressure

Molecular dynamics (MD) calculations were performed to reveal the effect of high pressure on the crystal of 1,3-diamino-2,4,6-trinitrobenzene (DATB). The coordinates of the individual atoms in the DATB crystal structure were obtained using X-ray diffraction analysis. The primary simulation cell consists of 54 molecules in a monoclinic cell, corresponding to 27 unit cells obtained by replicating the experimentally determined unit cell. The pressure dependence of intermolecular distance concerning hydrogen bonds in the DATB crystal was investigated in the range of 1 atm to 25.0 GPa by increasing the pressure at every 0.5 GPa. Intermolecular distances of the hydrogen bonds between the nitro and amino groups decrease with increasing pressure up to 25.0 GPa, except in the range of 7.5 to 8.5 GPa. A unique structural change in the DATB crystal occurred at ∼7.5 GPa. Intermolecular distances began to remarkably increase at 7.5 GPa and kept increasing until 8.5 GPa. To clarify the origin of this strange behavior, we used the same pressure regions as those above to analyze the changes in the dihedral angles defined by the plane of the nitro or amino group and by the aromatic rings of hydrogen bonds. The results showed a strong correlation between the increment of the intermolecular distances and the changes in the dihedral angles for these groups. Moreover, when the pressure dependence of the crystal parameter was analyzed, it was found that the a-axis length did not change despite the change in the lengths of the other two axes. The direction of the a axis corresponds to the direction of intermolecular hydrogen bond networks in the crystal. The results of the present MD calculations explained our previous results for Raman spectra measurements. Further analysis showed that these hydrogen bonds play an important role in stabilizing the energy change of the crystal system.