Novel polymerization of nitrogen in zinc nitrides at high pressures.

Nitrogen-rich compounds containing polynitrogen are attractive candidates for high-energy-density materials. In this work, using first-principles calculations and a particle swarm optimization structural search method, four novel nitrogen-rich structures are predicted at high pressures, i.e., two ZnNphases with the same space group1 (low-pressure phase LP-ZnNand high-pressure phase HP-ZnN),2-ZnNand2-ZnN, the energy density are estimated to be 1.41 kJ g, 1.88 kJ g, 4.07 kJ g, and 2.60 kJ g, respectively. LP-ZnN(54-72 GPa) and HP-ZnN(above 72 GPa) have the lowest enthalpies in all known ZnNphases, and the Nchains in LP-ZnNpolymerize into infinite nitrogen chains in HP-ZnNat 72 GPa, showing a narrow-band-gap-semiconductor to metallic phase transition. Interestingly,1-ZnNhas a superconducting transition temperature of 6.2 K at 50 GPa and 16.3 K at 100 GPa. In2-ZnNand2-ZnN, nitrogen atoms polymerize into three-dimensional network structures and network layers under high pressures. Those predicted structures may enrich the phase diagram of high-pressure zinc nitrides, and provide clues for synthesis and exploration of novel stable polymeric nitrogen.