Scholarlink

<p>Full-nitrogen energetic materials represent a breakthrough candidate for next-generation explosives and propellants, offering unparalleled energy density and zero-carbon-footprint decomposition. Through systematic density functional theory (DFT) calculations at the M06-2X/def2-TZVP level, key findings revealed that small full-nitrogen rings (<i>N</i> &lt; 10) achieve significant aromatic stabilization through π-electron delocalization (AV1245 index &gt; 3.0), while larger systems (<i>N</i> ≥ 10) completely lose aromatic character despite maintaining planar geometries due to pronounced electron localization. All neutral full- nitrogen molecules presented positive HOFs (359.4-3338&#xa0;kJ/mol at the M06-2X/def2-TZVP level), but with mediocre energetic density (1.661-1.886&#xa0;g/cm<sup>3</sup> at the M06-2X/def2-TZVP level). It was worth noting that the [N<sub>7</sub>]<sup>3−</sup> anion exhibited exceptional anti-aromatic characteristics (AICD-identified clockwise current) with uniform charge distribution (ESP variance = 0.0003 a.u.<sup>2</sup>), enabling formation of salts with record thermodynamic stability (∆H<sub>f,salt</sub> &lt; -129.7&#xa0;kJ/mol at MP2/def2-TZVP level). Non-covalent interaction (NCI) analysis confirmed spontaneous dimerization via π-π stacking and van der Waals interactions. Our findings proposed a novel design concept for next-generation energetic materials, which provides theoretical guidance for developing high-energy-density energetic materials with balanced stability and sensitivity.</p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Computational investigation of the [N7]3− anion and related full-nitrogen ring systems

  • 期刊论文

  • 发表日期：

    2025年12月17日

查看全文
  • Qian Zhang,
  • Tao Long,
  • Lan-Ying Xu,
  • Yan Huang

摘要

Full-nitrogen energetic materials represent a breakthrough candidate for next-generation explosives and propellants, offering unparalleled energy density and zero-carbon-footprint decomposition. Through systematic density functional theory (DFT) calculations at the M06-2X/def2-TZVP level, key findings revealed that small full-nitrogen rings (N < 10) achieve significant aromatic stabilization through π-electron delocalization (AV1245 index > 3.0), while larger systems (N ≥ 10) completely lose aromatic character despite maintaining planar geometries due to pronounced electron localization. All neutral full- nitrogen molecules presented positive HOFs (359.4-3338 kJ/mol at the M06-2X/def2-TZVP level), but with mediocre energetic density (1.661-1.886 g/cm3 at the M06-2X/def2-TZVP level). It was worth noting that the [N7]3− anion exhibited exceptional anti-aromatic characteristics (AICD-identified clockwise current) with uniform charge distribution (ESP variance = 0.0003 a.u.2), enabling formation of salts with record thermodynamic stability (∆Hf,salt < -129.7 kJ/mol at MP2/def2-TZVP level). Non-covalent interaction (NCI) analysis confirmed spontaneous dimerization via π-π stacking and van der Waals interactions. Our findings proposed a novel design concept for next-generation energetic materials, which provides theoretical guidance for developing high-energy-density energetic materials with balanced stability and sensitivity.