Wang Shaoqing, Huang Yan, Ma Qing, Chen Fu-Xue
School of Chemistry & Chemical Engineering, Beijing Institute of Technology (Liangxiang Campus), No. 8 Liangxiang East Road, Fangshan District, Beijing, 102488, China.
School of Chemistry and Chemical Engineering, Huanggang Normal University, Huanggang, 438000, China.
J Mol Model. 2025 Jun 4;31(7):183. doi: 10.1007/s00894-025-06401-z.
A series of tricyclic high energy density materials (HEDMs) incorporating diazole, triazole, and tetrazole frameworks were systematically investigated through density functional theory (DFT) calculations at the B3LYP/6-31G + + (d,p) and M06-2X/def2-SVP levels. Nitroform-based compounds and fluorodinitromethyl-substituted derivatives were found to exhibit superior densities compared to HMX. Notably, compound II-7 demonstrated the highest predicted density of 2.04 g cm⁻, along with optimal detonation performance (D = 9451 m s⁻, P = 42.57 GPa), surpassing that of HMX. Regarding heat of formation, the tetrazole-based compound III-1 exhibited the highest value of 844.42 kJ mol⁻, suggesting enhanced energy content. While nitroform groups improve performance, fluorine substitution offers better stability and sensitivity, representing an effective optimization strategy for energetic materials. Comparative analysis of structures with identical substituents but different parent ring frameworks reveals clear structure property relationships. The incorporation of nitrogen oxygen bonds is shown to significantly enhance performance characteristics.
Based on the DFT, molecular optimization and performance metrics analysis were all calculated using the Gaussian 09 package at B3LYP/6-31G + + (d,p) and M06-2X/def2-SVP levels. The electrostatic potential energy and other related calculations were computed using Multiwfn_3.8_dev software. The visualization of the weak interaction between dimers was accomplished using VMD 1.9.3 program.
通过在B3LYP/6-31G++(d,p)和M06-2X/def2-SVP水平上的密度泛函理论(DFT)计算，系统研究了一系列包含二唑、三唑和四唑骨架的三环高能量密度材料(HEDM)。发现基于硝基甲的化合物和氟二硝基甲基取代的衍生物与奥克托今相比具有更高的密度。值得注意的是，化合物II-7表现出预测的最高密度2.04 g cm⁻，同时具有最佳爆轰性能(D = 9451 m s⁻，P = 42.57 GPa)，超过了奥克托今。关于生成热，基于四唑的化合物III-1表现出最高值844.42 kJ mol⁻，表明能量含量增加。虽然硝基甲基团提高了性能，但氟取代提供了更好的稳定性和敏感性，这是高能材料的一种有效优化策略。对具有相同取代基但不同母环骨架的结构进行比较分析，揭示了明确的结构-性能关系。结果表明，氮氧键的引入显著提高了性能特征。
基于DFT，分子优化和性能指标分析均使用Gaussian 09软件包在B3LYP/6-31G++(d,p)和M06-2X/def2-SVP水平上进行计算。静电势能和其他相关计算使用Multiwfn_3.8_dev软件完成。二聚体间弱相互作用的可视化使用VMD 1.9.3程序完成。
