Ab initio calculations of reactive pathways for α-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (α-HMX)

被引:80
作者
Lewis, JP
Glaesemann, KR
VanOpdorp, K
Voth, GA
机构
[1] Univ Utah, Dept Chem, Salt Lake City, UT 84112 USA
[2] Univ Utah, Henry Eyring Ctr Theoret Chem, Salt Lake City, UT 84112 USA
关键词
D O I
10.1021/jp002173g
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Using the BLYP and B3LYP level of density functional theory, four possible decomposition reaction pathways of HMX in the gas phase were investigated: N-NO2 bond dissociation, HONO elimination, C-N bond scission of the ring, and the concerted ring fission. The energetics of each of these four mechanisms are reported. Dissociation of the N-NO2 bond is putatively the initial mechanism of nitramine decomposition in the gas phase. Our results find the dissociation energy of this mechanism to be 41.8 kcal/mol at the BLYP level and 40.5 kcal/mol at the B3LYP level, which is comparable to experimental results. Three other mechanisms are calculated and found at the BLYP level to be energetically competitive to the nitrogen-nitrogen bond dissociation; however, at the B3LYP level these three other mechanisms are energetically less favorable. It is proposed that the HONO elimination and C-N bond scission reaction of the ring would be favorable in the condensed phase.
引用
收藏
页码:11384 / 11389
页数:6
相关论文
共 40 条