为了探索合成和稳定聚合氮形式的分子或晶体的途径,基于第一性原理计算提出了两种基于N4分子合成高能量密度材料的方法:第一种方法是在单晶金属表面吸附N4(Td)分子;第二种方法是利用结构搜索获取稳定的N4相关结构.提出了P-43m-N4、P4/m-LiN4和Amm2-G/N4三种含有N4分子的晶体,并计算了它们的能量密度、热力学和动力学稳定性以及电子结构性质.结果表明,在超高真空和低温条件下,N4(Td)在金属表面可以通过失去Td对称而稳定.AIMD模拟结果表明,它们在50GPa、50或300K下是稳定的.通过N4与金属原子形成的配位键,聚合N4可以在高压下合成,并在低温条件下稳定.“,”To explore the routes for synthesizing and stabilizing polymeric nitrogen in molecules or crystals ,two methods for synthesizing high energy density materials (HEDM) based on N4 molecules were proposed based on the first-principles calcula-tions .The first route is to adsorb N4 (Td ) molecule on single crystal metal surfaces ,and the second method is to use structural search to obtain stable N4-related structures .Three N4-containing crystals ,P-43m-N4 ,P4/m-LiN4 and Amm2-G/N4 were pro-posed ,and their energy densities ,thermodynamic and kinetic stabilities ,as well as their electronic properties were calculated . The results show that under ultra-high vacuum and low temperature conditions ,N4 (Td ) can be stabilized by losing the Td sym-metry on the metal surfaces .AIMD simulations indicate that they are stable at 50 GPa and 50 or 300K .Through coordination bond between N4 and metal atoms ,polymerized N4 can be synthesized at high pressure and stabilized at low temperature con-ditions .