Shear-strain-induced structural and electronic modifications of the molecular crystal 1,1-diamino-2,2-dinitroethylene: Slip-plane flow and band gap relaxation

First-principles calculations of the structural and electronic properties of the deformed molecular crystal 1,1-diamino-2,2-dinitroethylene (FOX-7) under shear-strain loading are presented. The reaction of the crystal to applied shear-strain loading is found to be highly anisotropic. When the external loading is removed, the relaxation of the system is mainly defined by stretching, bending, and rotations of the NO2 groups of neighboring molecules from the two adjacent zigzag-shaped crystalline planes that were initially shifted. In general, the deformed molecular crystal relaxes to its initial, ideal crystalline FOX-7 structure. However, different planes remain shifted relatively to each other on vectors, which are typically incommensurated with any translational vector of the ideal crystal. This fact makes an existence of ideal crystals of this material quite problematic. We also found that no metallization occurs under shear-strain loading. We suggest that the considered mechanisms of the shear-strain relaxation of the structural and electronic degrees of freedom are typical for layered anisotropic molecular crystals, and that they should significantly affect their chemical reactivity, conductivity, optical properties, and initiation of detonation in energetic materials.