Phase transition-induced initial decomposition of nitrogen-rich binary CN compound 2,2′-azobis(5-azidotetrazole) and its precursor 2-amino-5-azidotetrazole via tetrazole ring opening under external electric fields: a comparative DFT-D study

A comparative DFT-D study was performed to investigate the external electric field-induced crystal structures, electronic features, Hirshfeld surfaces, vibrational properties and initial decomposition mechanisms of nitrogen-rich binary CN compound 2,2'-azobis(5-azidotetrazole) (C₂N₁₆) and its precursor 2-amino-5-azidotetrazole (CH₂N₈). The results show that there exist phase transitions at the critical points of 0.006 a.u. and 0.008 a.u. for CH₂N₈ and C₂N₁₆, respectively, which are embodied in various properties of these compounds and induce their initial decomposition of the tetrazole ring opening via the breaking of N-N single bonds. The analysis of band gaps and density of states suggests the external electric field-induced enhancing ability for electron transition from the occupied orbitals to empty ones and N-N bond breaking may be the initial decomposition pathway for them. The variations in Hirshfeld surfaces indicate the spatial change and adjustment of non-bonding interactions in the two crystals. The discussions on vibrational properties indicate that IR characteristic peaks of all vibrational modes in the two crystals show a gradual red shift toward a low frequency region. The external electric field-induced initial decomposition pathways of both crystals are tetrazole ring opening via the breaking of a N-N single bond. Our findings provide insights for a comprehensive understanding of external electric field-induced phase transition and initial decomposition mechanisms of nitrogen-rich binary CN energetic compounds.