A novel all-nitrogen molecular crystal N16 as a promising high-energy-density material,Dalton Transactions

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A novel all-nitrogen molecular crystal N16 as a promising high-energy-density material
Dalton Transactions ( IF 3.5 ) Pub Date : 2022-05-23 , DOI: 10.1039/d2dt00820c
Lei Zhao _{1,

2} , Shijie Liu _{3,

4} , Yuanzheng Chen ₅ , Wencai Yi ₆ , Darlar Khodagholian ₂ , Fenglong Gu ₇ , Eric Kelson ₂ , Yonghao Zheng ₈ , Bingbing Liu ₄ , Mao-Sheng Miao ₂

Affiliation

College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, P. R. China.
Department of Chemistry & Biochemistry, California State University Northridge, Northridge, CA, 91330, USA.
School of Physics and Engineering, and Henan Key Laboratory of Photoelectric Energy Storage Materials and Applications, Henan University of Science and Technology, Luoyang 471003, P. R. China.
State Key Laboratory of Superhard Materials, Jilin University, Changchun 130012, P. R. China.
School of Physical Science and Technology, Key Laboratory of Advanced Technologies of Materials, Ministry of Education of China, Southwest Jiaotong University, Chengdu 610031, P. R. China.
School of Physics and Physical Engineering, Qufu Normal University, Qufu, 273165, P. R. China.
Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment, South China Normal University, Guangzhou 510006, P. R. China.
School of Optoelectronic Science and Engineering, University of Electronic Science and Technology of China (UESTC), Chengdu 610054, P. R. China.

All-nitrogen solids, if successfully synthesized, are ideal high-energy-density materials because they store a great amount of energy and produce only harmless N₂ gas upon decomposition. Currently, the only method to obtain all-nitrogen solids is to apply high pressure to N₂ crystals. However, products such as cg-N tend to decompose upon releasing the pressure. Compared to covalent solids, molecular crystals are more likely to remain stable during decompression because they can relax the strain by increasing the intermolecular distances. The challenge of such a route is to find a molecular crystal that can attain a favorable phase under elevated pressure. In this work, we show, by designing a novel N₁₆ molecule (tripentazolylamine) and examining its crystal structures under a series of pressures, that the aromatic units and high molecular symmetry are the key factors to achieving an all-nitrogen molecular crystal. Density functional calculations and structural studies reveal that this new all-nitrogen molecular crystal exhibits a particularly slow enthalpy increase with pressure due to the highly efficient crystal packing of its highly symmetric molecules. Vibration mode calculations and molecular dynamics (MD) simulations show that N₁₆ crystals are metastable at ambient pressure and could remain inactive up to 400 K. The initial reaction steps of the decomposition are calculated by following the pathway of the concerted excision of N₂ from the N₅ group as revealed by the MD simulations.

中文翻译：

一种新型全氮分子晶体 N16 作为一种有前途的高能量密度材料

如果合成成功，全氮固体是理想的高能量密度材料，因为它们储存了大量的能量并且在分解时仅产生无害的N _2气体。_{目前，获得全氮固体的唯一方法是对N 2}晶体施加高压。但是，cg-N 等产品在释放压力时往往会分解。与共价固体相比，分子晶体在减压过程中更可能保持稳定，因为它们可以通过增加分子间距离来放松应变。这种路线的挑战是找到一种可以在高压下获得有利相的分子晶体。在这项工作中，我们通过设计一种新颖的 N ₁₆分子（三戊唑胺）并在一系列压力下检查其晶体结构，发现芳香单元和高分子对称性是实现全氮分子晶体的关键因素。密度泛函计算和结构研究表明，由于其高度对称的分子的高效晶体堆积，这种新的全氮分子晶体表现出特别缓慢的焓随压力增加。振动模式计算和分子动力学 (MD) 模拟表明，N ₁₆晶体在环境压力下是亚稳态的，并且可以在高达 400 K 的温度下保持非活性。分解的初始反应步骤是通过遵循 N ₂的协同切除路径来计算的。 N ₅MD模拟显示的组。

更新日期：2022-05-23

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