稠环类1,2,4,5-四嗪衍生物结构和性能的理论研究  

Theoretial Study on Structure and Properties of Polycyclic Derivatives of 1,2,4,5-Tetrazine Based High Energy Density Materials

作　　者：张驰[1] 陈沫[1] 陈湘[1] 张聪[1] 宋纪蓉[1,2] 马海霞[1] 

机构地区：[1]西北大学化工学院,陕西西安710069 [2]北京故宫博物院文保科技部,北京100080

出　　处：《含能材料》2017年第4期273-281,共9页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金项目(21673179)资助

摘　　要：运用密度泛函理论DFT-w B97/6-31+G**方法研究了14种稠环类1,2,4,5-四嗪衍生物的几何结构、前线轨道能量和生成焓(ΔH_f)。在此基础上运用Kamlet-Jacobs方程估算衍生物的爆轰性能;运用统计热力学,计算了标题化合物在200~800 K的热力学性质;比较了1,2,4,5-四嗪衍生物的生成焓和爆轰性能。结果表明,稠环四嗪衍生物爆速(D)和爆压(p)与所含N原子数具有良好的一次线性相关关系,其生成焓为527.49~1122.53 k J·mol^(-1),爆速为5.59~8.65 km·s^(-1);随温度升高,标准摩尔热容(Cp,m)、标准摩尔熵(Sm)和标准摩尔焓(Hm)逐渐增大。化合物T7(C_2N_7H_2)和T72(C_2N_(10)H_2)可以作为高能量密度材料(HEDM)候选物。The geometrical structures, front orbital energies and enthalpies of formation （△Hf） of 14 kinds of 1,2,4,5-tetrazine polycyclic ring derivatives were studied using density functional theory （DFT） and wB97/6-31 ＋G ＊＊ basis set level. The detonation performances of these derivatives were estimated by Kamlet-Jacobs equation. The thermodynamic properties of these compounds at different temperatures from 200K to 800K were obtained by statistic thermodynamics. The detonation properties and heat of formation of these 1,2,4,5-tetrazine derivatives were also compared. Results show that the detonation velocity （D） and detonation pressure （p） have good linear correlation with the numbers of nitrogen, and their △Hf are between 527.49 kJ . mol-1 and 1122.53 kJ . mol-1 and the detonation velocities are between 5.59 and 8.65 km . s-1 . The values of the standard heat capacity （ Cρ,m ） , standard molar entropy （ Sm ） and the standard enthalpy （ Hm ） gradually increase with the temperature. The compounds T7 （ C2 N7 H2 ） and T72 （ C2 N10 H2 ） may be considered as potential candidates for energetic materials.

关 键 词：密度泛函理论(DFT) 1 2 4 5-四嗪衍生物 生成焓 爆轰性能 热力学性质 

分 类 号：TQ560.1[化学工程—炸药化工] O626[理学—有机化学]