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<p>With the increasing demand for energetic materials featuring high energy density, enhanced safety, and superior thermal resistance, achieving a balance between energetic output and thermal robustness remains a major challenge in developing nitrogen-rich fused heterocyclic compounds. In this work, benzimidazole- and pyrazolo[3,4-d]pyridazine-based energetic derivatives were selected as model systems to systematically explore how nitro and amino substituents influence electronic characteristics, weak intermolecular interactions, and the initial thermal decomposition processes through density functional theory calculations.</p><p>LBO and BDE analyses indicate that amino substitution enhances the stability of functional-group linkage bonds. ESP and IRI analyses reveal that amino groups promote electron delocalization, produce a more uniform charge distribution, and strengthen hydrogen bonding and weak interactions. Hirshfeld surface analysis further shows that amino substitution increases O···H hydrogen-bond-related contacts while reducing H···H repulsive interactions. Transition-state calculations demonstrate that nitro-substituted systems preferentially undergo NO₂–ONO isomerization, whereas amino substitution significantly enhances the competitiveness of hydrogen-transfer pathways.</p><p>Overall, the results suggest that amino functionalization, together with its cooperative interaction with neighboring nitro groups, can improve the thermal stability of fused energetic systems through the combined effects of enhanced bond stability, promoted electron delocalization, strengthened weak interactions, and altered kinetic competition among initial decomposition pathways. This work provides theoretical insight into the molecular-level regulation of thermal stability in nitrogen-rich fused heterocyclic energetic materials.</p>

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Functional group effects on thermal stability and initial decomposition behavior of nitrogen-rich fused heterocyclic energetic materials: a DFT study

  • 期刊论文

  • 发表日期：

    2026年7月13日

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  • Yuqin Chu,
  • Peng Zhang,
  • Yang Zhu,
  • Peng Ma,
  • Congming Ma

摘要

With the increasing demand for energetic materials featuring high energy density, enhanced safety, and superior thermal resistance, achieving a balance between energetic output and thermal robustness remains a major challenge in developing nitrogen-rich fused heterocyclic compounds. In this work, benzimidazole- and pyrazolo[3,4-d]pyridazine-based energetic derivatives were selected as model systems to systematically explore how nitro and amino substituents influence electronic characteristics, weak intermolecular interactions, and the initial thermal decomposition processes through density functional theory calculations.

LBO and BDE analyses indicate that amino substitution enhances the stability of functional-group linkage bonds. ESP and IRI analyses reveal that amino groups promote electron delocalization, produce a more uniform charge distribution, and strengthen hydrogen bonding and weak interactions. Hirshfeld surface analysis further shows that amino substitution increases O···H hydrogen-bond-related contacts while reducing H···H repulsive interactions. Transition-state calculations demonstrate that nitro-substituted systems preferentially undergo NO₂–ONO isomerization, whereas amino substitution significantly enhances the competitiveness of hydrogen-transfer pathways.

Overall, the results suggest that amino functionalization, together with its cooperative interaction with neighboring nitro groups, can improve the thermal stability of fused energetic systems through the combined effects of enhanced bond stability, promoted electron delocalization, strengthened weak interactions, and altered kinetic competition among initial decomposition pathways. This work provides theoretical insight into the molecular-level regulation of thermal stability in nitrogen-rich fused heterocyclic energetic materials.