Ambient-Stable Polymeric Nitrogen Achieved through Multi-Stage Computational Design

Abstract The four-decade quest for synthesizing ambient-stable polymeric nitrogen, a promising high-energy-density material, remains an unsolved challenge in materials science. We develop a multi-stage computational strategy employing density functional tight-binding-based rapid screening combined with density functional theory refinement and global structure searching, effectively bridging computational efficiency with quantum accuracy. This integrated approach identifies four novel polymeric nitrogen phases ( Fddd , P 3221, <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mrow> <mml:mi>I</mml:mi> <mml:mover accent="true"> <mml:mn>4</mml:mn> <mml:mo stretchy="false">¯</mml:mo> </mml:mover> <mml:mi>m</mml:mi> <mml:mn>2</mml:mn> </mml:mrow> </mml:math> , and P 6522) that are thermodynamically stable at ambient pressure. Remarkably, the helical P 6522 configuration demonstrates exceptional thermal resilience up to 1500 K, representing a predicted polymeric nitrogen structure that maintains stability under both atmospheric pressure and high-temperature extremes. Our methodology establishes a paradigm-shifting framework for the accelerated discovery of metastable energetic materials, resolving critical bottlenecks in theoretical predictions while providing experimentally actionable targets for polymeric nitrogen synthesis.