稠环类1,2,4,5-四嗪衍生物结构和性能的理论研究

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。

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

The geometrical structures,front orbital energies and enthalpies of formation(ΔHf) 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 ΔHf 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 (Cp,m),standard molar entropy (Sm) and the standard enthalpy (Hm) gradually increase with the temperature.The compounds T7(C2N7H2) and T72(C2N10H2) may be considered as potential candidates for energetic materials.