Super high-energy density single-bonded trigonal nitrogen allotrope—a chemical twin of the cubic gauche form of nitrogen

Abstract

A new ambient-pressure metastable single-bonded 3D nitrogen allotrope (TrigN) of trigonal symmetry (space group R) was calculated using density functional theory (DFT). A comprehensive characterization of this material, comprising thermodynamic, elastic, and spectral (vibrational, UV-vis absorption, and nuclear magnetic resonance) properties, was performed. Using high-throughput band structure calculation, the TrigN phase was characterized as an insulator with an indirect band gap of 2.977 eV. Phonon dispersion calculations justified that this structure is vibrationally stable at ambient pressure. The calculated Raman activities at the Γ-point demonstrated a rich pattern, whereas no relatively intense transitions were observed in its IR absorption spectrum. The TrigN material is almost transparent to visible light as well as to ultraviolet A and B. The main absorption peaks appeared within the range of 50–200 nm. The electron arrangement of the nitrogen nuclei in the studied nitrogen allotrope is much denser compared to that of the molecular nitrogen, which is in agreement with the calculated magnetic shielding tensor values. Robust mechanical stability is revealed from the elastic constants calculation. Due to strong anisotropy, the values of the Young's moduli vary from 281 to 786 GPa. A huge amount of internal energy is enclosed in the TrigN material. Upon decomposition to molecular nitrogen, the energy release is expected to be 11.01 kJ g⁻¹ compared to the value of 10.22 kJ g⁻¹ for the cubic gauche form of nitrogen. The TrigN allotrope possesses unique detonation characteristics with a detonation pressure of 146.06 GPa and velocity of 15.86 km s⁻¹.