Density functional theory study of high‐pressure effect on crystalline 4,4′,6,6′‐tetra(azido)hydrazo‐1,3,5‐triazine

Periodic density functional theory calculations are performed to study the hydrostatic compression effects on the structure, electronic, and thermodynamic properties of the energetic polyazide 4,4′,6,6′‐tetra(azido)hydrazo‐1,3,5‐triazine (TAHT) in the range of 0?100 GPa. At the ambient pressure, the local density approximation/Ceperley‐Alder exchange‐correlation potential parameterized by Perdew and Zunger relaxed crystal structure compares well with the experimental results. The predicted heat of sublimation is 38.68 kcal/mol, and the evaluated condensed phase of formation (414.04 kcal/mol) approximates to the experimental value. The detonation velocity and detonation pressure for the solid TAHT are calculated to be 7.44 km/s and 23.71 GPa, respectively. When the pressure is exerted less than 35 GPa, the crystal structure and geometric parameters change slightly. However, at 36 GPa, the molecular structure, band structure, and density of states change abnormally because of the azide‐tetrazole transformation that has not been observed in gas phase or polar solvents. The azido group cyclizes to form a five‐membered tetrazole ring that is coplanar with the riazine ring and contributes to a larger conjunction system. As the pressure augments further to 80 GPa, the hydrogen transfer is found and a new covalent bond H2? N9 is formed. In the studied pressure range, the band gap decreases generally except for some breaks due to the molecular transformation and drops to nearly zero at 100 GPa, which means the electronic character of the crystal changes toward a metallic system. An analysis of the electronic structure shows that an applied pressure increases the impact sensitivity of TAHT. © 2012 Wiley Periodicals, Inc.