Realizing stable zig-zag polymeric nitrogen chains in P-N compounds

Abstract: The zig-zag Nitrogen (N) chain similar to the Ch-N structure has long been considered a potential high energy density structure. However, all previously predicted zig-zag N chain structures similar to Ch-N exhibit imaginary frequencies in their phonon spectra at 0 GPa. Here, we conducted a systematic investigation of P-N compounds using first-principles calculations, uncovering a series of structurally similar stable phases, C2/m-PNx (x = 6, 8, 10, 12, 14), in which N forms zig-zag N chains similar to those in Ch-N. In P-N compounds, the longest zig-zag N chain that can theoretically remain stable under ambient pressure is the N chain composed of 14 N atoms in C2/m-PN14. If the N chain continues to grow, inter-chain vibrational imaginary frequencies will arise in the system. Notably, N chains with an even number of atoms are more likely to be energetically favorable. The five C2/m-PNx phases and one metastable phase (R-PN6) exhibit both remarkable stability and excellent detonability at ambient pressure, positioning them as promising candidates for high-energy-density materials. In addition, the R-PN6 is the first structure to stabilize the N6 ring through covalent bonding, with the covalent network contributing to its high hardness (47.59 GPa).