NO2,OH和OH^-对环四甲撑四硝胺初始热解的影响  

Effects of NO_2,OH and OH^- on the Initial Pyrolysis of β-Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine

作　　者：姜富灵[1,2] 翟高红[1,2] 丁黎[3] 岳可芬[1,2] 刘妮[1,2] 史启祯[1,2] 文振翼[1,2] 

机构地区：[1]合成与天然功能分子化学教育部重点实验室,西安710069 [2]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 [3]西安近代化学研究所,西安710065

出　　处：《物理化学学报》2010年第2期409-414,共6页Acta Physico-Chimica Sinica

基　　金：陕西省教育厅专项科研计划项目(09JK789)资助~~

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200kJ.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.The structures of β-octahydro-l,3,5,7-tetranitro-l,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 （DPT）. 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.

关 键 词：密度泛函理论 HMX 高氯酸铵 热裂解 解离能 

分 类 号：TQ560.1[化学工程—炸药化工]