化学学报 ›› 2011, Vol. 69 ›› Issue (06): 610-616. 上一篇    下一篇

研究论文

叠氮唑类高氮含能化合物的理论研究

牛晓庆1,张建国*,1,王颖1,陈陶平2,张绍文3,张同来1,周遵宁1,杨利1   

  1. (1北京理工大学爆炸科学与技术国家重点实验室 北京 100081)
    (2邯郸学院图书馆 邯郸 056002)
    (3北京理工大学理学院 北京 100081)
  • 投稿日期:2010-08-28 修回日期:2010-11-01 发布日期:2010-11-18
  • 通讯作者: 张建国 E-mail:zhangjianguobit@yahoo.com.cn
  • 基金资助:

    国家自然科学基金项目; 国家自然科学基金委-中国工程物理研究院联合基金; 教育部新世纪优秀人才支持计划

Theoretical Studies of Azide-Azole Nitrogen-Rich Energetic Compounds

Niu Xiaoqing1 , Zhang Jianguo*,1 Wang Ying1 Chen Taoping2 Zhang Shaowen3 Zhang Tonglai1 Zhou Zunning1 Yang Li1   

  1. (1 State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081)
    (2 Library of Handan College, Handan 056002)
    (3 School of Science, Beijing Institute of Technology, Beijing 100081)
  • Received:2010-08-28 Revised:2010-11-01 Published:2010-11-18
  • Contact: Jianguo Zhang E-mail:zhangjianguobit@yahoo.com.cn

基于2-叠氮-1,3-咪唑、3-叠氮-1,2,4-三唑和5-叠氮-1氢-四唑的晶体结构数据, 自行设计了同系列化合物叠氮-五唑的分子结构. 采用B3LYP方法, 选取6-311++G**基组, 对叠氮唑类化合物进行优化并得到了稳定的分子构型, 结构参数与现有的实验数据相符. 故在此水平下对此系列化合物进行红外振动、键级及自然键轨道分析, 计算结果表明, 所有化合物均无虚频, 为势能面上的稳定结构, 分子中存在一个大的共轭体系|根据前线轨道能隙差(ΔEL-H)得到4种化合物的热稳定顺序为: 5-叠氮-1-氢-四唑>3-叠氮-1,2,4-三唑>叠氮-五唑>2-叠氮-1,3-咪唑|计算得到的生成热、密度、爆速爆压均随着体系中含氮量的增加而增加, 即叠氮-五唑的爆速、爆压最大, 爆速达到了9897 m•s-1, 爆压达到了46.0 GPa, 在含能材料领域具有潜在的应用前景.

关键词: 高氮化合物, 结构优化, 振动分析, 生成热, 爆速, 爆压

Based on the crystal data of 2-azido-1,3-imidazole, 3-azido-1,2,4-triazole and 5-azido-1H-tetrazole, a novel of azido-pentazole was firstly devised. The most stable molecular geometries of azide-azole compounds were obtained using B3LYP methods with 6-311++G** basis set. Compared with existing experimental data, B3LYP/6-311++G** is the suitable basis set for compounds. Moreover, IR spectra and bond order of azide-azole nitrogen-rich energetic compounds were obtained. The results show that they have not imaginary frequencies, so they were stable on the potential energy surface. There is a great conjugate system among molecular structures. The frontier orbital energies and their differences predict that the stabilities of the title compounds decrease in the order: 5-azido-1H-tetrazole>3-azide-1,2,4-triazole>azido-pentazole>2-azido-1,3-imidazole. The results show that heat of formation, density, detonation velocity and detonation pressure of the title compounds linearly increase with increasing nitrogen mass fraction in the system. Azido-pentazole with detonation velocity of 9897 m•s-1, and the detonation pressure of 46.0 GPa, which has potential applications in the high energy density materials.

Key words: nitrogen-rich compounds, molecular geometry, frequency analysis, heat of formation, detonation velocity, detonation pressure