Acta Phys. -Chim. Sin. ›› 2010, Vol. 26 ›› Issue (02): 409-414.doi: 10.3866/PKU.WHXB20100128

• QUANTUM CHEMISTRY AND COMPUTATION CHEMISTRY • Previous Articles     Next Articles

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

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