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化学学报
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化学学报 ›› 2011, Vol. 69 ›› Issue (14): 1627-1638. 上一篇    下一篇

研究论文

B炸药主要组分TNT和RDX分子间相互作用的理论研究

牛晓庆1，张建国*,1，冯晓军2，陈鹏万1，张同来1，王世英2，张绍文3，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西安近代化学研究所 西安 710065)
    (3北京理工大学理学院 北京 100081)
  • 投稿日期:2010-12-01 修回日期:2011-02-22 发布日期:2011-03-17
  • 通讯作者: 张建国 E-mail:zhangjianguobit@yahoo.com.cn
  • 基金资助:

    教育部新世纪优秀人才支持计划资助项目

Theoretical Investigation on Intermolecular Interactions Between The Ingredients TNT and RDX of Composition B

Niu Xiaoqing1 Zhang Jianguo*,1 Feng Xiaojun2 Chen Pengwan1 Zhang Tonglai1 Wang Shiying2 Zhang Shaowen3 Zhou Zunning1 Yang Li1   

  1. (1 State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081)
    (2 Xian Modern Chemistry Research Institute, Xian 710065)
    (3 School of Science, Beijing Institute of Technology, Beijing 100081)
  • Received:2010-12-01 Revised:2011-02-22 Published:2011-03-17
  • Contact: Jianguo Zhang E-mail:zhangjianguobit@yahoo.com.cn

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在B3LYP/6-31G(d)水平上研究了B炸药的主要成分——2,4,6-三硝基甲苯(TNT)与环三亚甲基三硝胺(RDX)分子间的相互作用, 得到了10种TNT＋RDX的全优化构型. 讨论了稳定构型在几何参数、稳定性、红外光谱和电荷分布上的差异. 借助自然键轨道(NBO)理论揭示了TNT与RDX分子间相互作用的本质, 主要由氢键所贡献. 分子间相互作用能在－3.930～－14.652 kJ•mol－1之间, 经基组叠加误差(BSSE)校正, 相互作用能顺序为VI＞III＞V＞IV＞X＞I＞IX＞II＞VII＞VIII. 对全优化构型进行了热力学性质的分析, 探讨了由单体分子形成混合体系的热力学性质的变化, 结果发现, 形成分子间氢键是个放热过程. 运用Kamlet-Jacobs方程基于理论密度(ρ)估算了混合体系TNT＋RDX的爆轰性质爆速(D)和爆压(p), 与文献值进行比较表明理论计算方法和结果是可靠的.

关键词: B炸药, 分子间相互作用, 密度泛函理论, 结构优化, 振动分析, 热力学性质, 爆轰性质

The intermolecular interaction between 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro- 1,3,5-triazine (RDX), which were the main components of Composition B, were studied at B3LYP/6-31G(d) level. The optimized conformations of the ten forms were obtained. The geometrical parameters, stability, electronic structures and harmonic vibrational frequencies were investigated for the optimized structure at the same level. Natural bond orbital (NBO) analyses were performed to reveal the origin of intermolecular interaction between TNT and RDX. The hydrogen bonds contribute to the interaction energies dominantly. The intermolecular interactions are within a range of －3.930～－14.652 kJ•mol－1, and the binding energy corrected for the basis set superposition error (BSSE) is in the order of VI＞III＞V＞IV＞X＞I＞IX＞II＞VII＞VIII. The changes of thermodynamic properties from monomer to complexes were discussed. It can be found that the formation of hydrogen bonds is exothermic process. Finally, the detonation performances were estimated by using the Kamlet-Jacobs equation. The reliability of this theoretical method and results were tested by comparing the theoretical values of ρ, p and D with experimental or referenced values.

Key words: composition B, intermolecular interaction, density functional theory, molecular geometry, vibrational analysis, thermodynamic property, detonation performance