Structural stability, vibrational and bonding properties of potassium 1,1$'$-dinitroamino-5,5$'$ bistetrazolate: An emerging green primary explosive

Abstract

Potassium 1,1$'$-dinitroamino-5,5$'$ bistetrazolate (K$_2$DNABT) is a nitrogen rich (50.3 $\%$ by weight, \ce{K2C2N12O4}) green primary explosive with high performance characteristics namely velocity of detonation (D = 8.33 km/s), detonation pressure (P = 31.7 GPa) and fast initiating power to replace existing toxic primaries. In the present work, we report density functional theory (DFT) calculations on structural, equation of state, vibrational spectra, electronic structure and absorption spectra of K$_2$DNABT. We have discussed the influence of weak dispersive interactions on structural and vibrational properties through the DFT-D2 method. We find anisotropic compressibility (b $<$ a $<$ c) from pressure dependent structural properties. The predicted bulk modulus reveals that the material is harder than cyanuric triazide (\ce{C3N12}) and softer than lead azide (\ce{Pb(N3)2}). A complete assignment of all vibrational modes has been made and compared with the available experimental results. The calculated zone centre IR and Raman frequencies show a blue-shift which leads to a hardening of the lattice upon compression. In addition, we have also calculated the electronic structure and absorption spectra using the recently developed Tran Blaha-modified Becke Johnson potential. It is found that K$_2$DNABT is a direct band gap insulator with a band gap of 3.87 eV and the top of the valence band mainly dominated by $2p$-states of oxygen and nitrogen atoms. K$_2$DNABT exhibits mixed ionic (between potassium and tetrazolate ions) and covalent character within tetrazolate molecule. The presence of ionic bonding suggests that the investigated compound is relatively stable and insensitive than covalent primaries. From the calculated absorption spectra, the material is found to decompose under ultra-violet light irradiation.