物理化学学报 >> 2010, Vol. 26 >> Issue (02): 409-414.doi: 10.3866/PKU.WHXB20100128

量子化学及计算化学 上一篇    下一篇

NO2, OH和OH-对环四甲撑四硝胺初始热解的影响

姜富灵, 翟高红, 丁黎, 岳可芬, 刘妮, 史启祯, 文振翼   

  1. 合成与天然功能分子化学教育部重点实验室, 西安 710069; 西北大学化学与材料科学学院, 陕西省物理无机化学重点实验室, 西安 710069; 西安近代化学研究所, 西安 710065
  • 收稿日期:2009-06-12 修回日期:2009-09-30 发布日期:2010-01-26
  • 通讯作者: 翟高红 E-mail:zgh@nwu.edu.cn

Effects of NO2, OH and OH- on the Initial Pyrolysis of β-Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine

JIANG Fu-Ling, ZHAI Gao-Hong, DING Li, YUE Ke-Fen, LIU Ni, SHI Qi-Zhen, WEN Zhen-Yi   

  1. Key Laboratory of Synthetic and Natural Functional Molecular Chemistry of Ministry of Education, Xi'an 710069, P. R. China; Shaanxi Key Laboratory of Phsico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi'an 710069, P. R. China; Xi'an Modern Chemistry Research Institute, Xi'an 710065, P. R. China
  • Received:2009-06-12 Revised:2009-09-30 Published:2010-01-26
  • Contact: ZHAI Gao-Hong E-mail:zgh@nwu.edu.cn

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摘要：

在密度泛函理论的(DFT)B3LYP/6-31g(d)水平上, 优化得到了环四甲撑四硝胺(β-HMX)及其与高氯酸铵(AP)裂解产物NO2、OH及OH-分别形成复合物的各种稳定构型, 计算了β-HMX及各复合物中最弱的N—NO2键解离能. 结果发现: β-HMX与NO2、OH结合后构型变化不是很大, 但对称性降低; β-HMX与OH-结合后, HMX构型发生较大变化, 原有的对称性明显遭到破坏. 计算表明: NO2易与HMX骨架环上亚甲基(—CH2—)中的H作用,“置换”出H而引发HMX的热解, 从而改变了HMX的初始分解通道; OH对HMX的N—NO2键解离影响不大, 而OH-与β-HMX结合后其N—NO2键解离能比β-HMX降低近200 kJ·mol-1, 表明OH-对其裂解有明显的促进作用. NO2、OH-的存在可使HMX的分解温度大大降低.

关键词: 密度泛函理论, HMX, 高氯酸铵, 热裂解, 解离能

Abstract:

The structures of β-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (β-HMX) and its complexes with the pyrolysis products (NO2, OH, OH-) of ammonium perchlorate (AP) were optimized at the B3LYP/6-31g(d) level of density functional theory (DFT). We obtained bond dissociation energies for N—NO2 in β-HMX and its complexes. We found that the geometrical configurations of HMX in the complexes with NO2 and OH were similar to the β-HMX structure but that the intrinsic symmetry decreases. The configurations of the OH- complexes are different and the original Ci symmetry is lost. Results further indicate that NO2 can easily capture a H from methylene on the HMX ring, which changes the initial pyrolysis channel of HMX. The influence of OH is negligible. The N—NO2 bond dissociation energies of OH- complexes decrease by about 200 kJ·mol-1 in comparison with that of β-HMX, which indicates that OH- can clearly promote the initial pyrolysis of β-HMX. The existence of NO2 and OH- can decrease the decomposition temperature of HMX greatly.

Key words: Density functional theory, HMX, Ammoniumperchlorate, Pyrolysis, Bond dissociation energy

MSC2000: 

  • O641