The high-pressure equation of state (EOS) of energetic materials (EMs) is important for continuum and mesoscale models of detonation performance and initiation safety. Obtaining a high-fidelity EOS of the insensitive EM 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) has proven to be difficult because of challenges in experimental characterization at high pressures (HPs). In this work, powder X-ray diffraction patterns were fitted using the recently discovered monoclinic I2/a phase above 4 GPa, which shows that TATB is less compressible than when indexed with the triclinic P1̅ phase. First-principles calculations were performed with Perdew–Burke–Ernzerhof (PBE) and PBE0 functionals including thermal effects using the P1̅ phase. PBE0 improves the description of hydrogen bonding and thus predicts accurate planar a and b lattice parameters under ambient conditions. However, discrepancies in the predicted lattice parameters above 4–10 GPa compared with experimental measurements indexed with P1̅ are further evidence of a structural modification at high pressure. Layer sliding defects are formed during molecular dynamics simulations, which induces an anharmonic effect on the thermal expansion of the c lattice parameter. In short, the results provide several insights into determining high-fidelity EOS parameters for TATB and other molecular crystals.

Brad A. Steele, Elissaios Stavrou, Vitali B. Prakapenka, Matthew P. Kroonblawd, I-Feng W. Kuo, High-Pressure Equation of State of 1,3,5-triamino-2,4,6-trinitrobenzene: Insights into the Monoclinic Phase Transition, Hydrogen Bonding, and Anharmonicity,  (2020) The Journal of Physical Chemistry A Article ASAP abstract

Conventional unit cell for the P1̅ phase of TATB under ambient conditions and corresponding crystallographic lattice vectors. Grey spheres are carbon atoms, white-pink spheres are hydrogen atoms, blue spheres are nitrogen atoms, and red spheres are oxygen atoms. The image is created using VESTA.