Lanthanium Nitride LaN₉ Featuring Azide Units: the First Metal Nine-nitride as High-energy Density Material

High-pressure phase diagrams of the La–N binary system were systematically constructed using the CALYPSO method and first-principles calculations. In addition to the pressure-induced La–N compounds reported previously, we have uncovered a hitherto unknown LaN9 structure in Pm symmetry stabilized within a narrow pressure range of 20–24.5 GPa. Notably, LaN9 stands as the first thermodynamically stable metal nine-nitrogen compound, featuring centrosymmetric linear N3 anion units and an edge-sharing LaN12 icosahedron. Charge transfer between the La and N atoms plays a crucial role in facilitating structural stability. Furthermore, we identified a novel Cm phase for LaN8, which has a lower enthalpy compared to the previously reported phase. N atoms in Cm LaN8 are polymerized into infinite N∞ chains. Calculations demonstrate the potential recoverability of LaN9 and Cm LaN8 under atmospheric conditions while preserving their initial polynitrogen configuration. From the perspective of detonation pressure and detonation velocity, LaN9 and Cm LaN8 exhibit excellent explosive performance in comparison to TNT and HMX, with estimated energy densities of 0.9 and 1.54 kJ g−1, respectively, indicating their potential utility as high-energy-density materials.