Pressure-Stabilized New Phase of CaN₄*

We propose a new CaN₄ high pressure structure with the P2₁/m space group. The P2₁/m-CaN₄ structure is constituted by the infinite armchair N-chain. The dynamical stability and mechanical stability are verified by the calculations of phonon dispersion curves and elastic constants. The enthalpy difference calculation shows that the P2₁/m phase is more stable than the reported P4₁2₁2 phase. The advantaged properties of P2₁/m-CaN₄, such as high nitrogen content (58.3%) and low polymerization pressure (18.3 GPa), allow it to be a potential high energy material. Band structure calculation shows that the P2₁/m-CaN₄ structure is a metallic phase. The nonpolar covalent single N–N bond is a sigma bond. The charge transfer between the Ca and N atoms results in an ionic bond interaction.