二硝基芳杂环并哒嗪化合物结构和性能的理论计算

摘要

Three dinitro heteroaromatic ring-fused pyridazines,4,7-dinitrofurazano[3,4-d]pyridazine (DNFP),4,7-dinitrofuroxano[3,4-d]pyridazine (DNFOP)and 5,8-dinitropyridazino [4,5-e][1 ,2,3,4 ]tetrazine 1,3-dioxide (DNPTDO)were designed.On the basis of the stable geometries optimized at B3LYP/6-31G** theoretical level, the Wiberg bond order,bond dissociation energy (BDE),electrostatic potential,theoretical density and solid state phase heats of formation of title compounds were calculated at the same theoretical level.The detonation velocities (D),detonation pressures (p )and the performances of these compounds as monopropellants were predicted by Kamlet-Jacobs formula and the minimum free energy method,respectively.The results show that the BDE,ρ,D , and p of DNFOP are 80.37 kJ/mol,1.939 g/cm3 ,9 151 m/s,and 39.54 GPa,respectively,and the BDE,ρ,D ,and p of DNPTDO are 208.59 kJ/mol,1 .942 g/cm3 ,9 235 m/s,and 40.30 GPa,respectively,while DNFP presents relatively lower detonation velocity (8 811 m/s)and detonation pressure (36.27 GPa).As monopropellants,specific impulse of DNFP,DNFOP and DNPTDO are higher than that of RDX by 97.6,120.6 and 140.6 N·s/kg,respectively.%设计了3种二硝基芳杂环并哒嗪化合物：4，7-二硝基呋咱并[3，4-d]哒嗪（DNFP）、4，7-二硝基氧化呋咱并[3，4-d]哒嗪（DNFOP）和5，8-二硝基哒嗪并[4，5-e][1，2，3，4]-四嗪1，3-二氧化物（DNPTDO）。采用密度泛函理论的 B3LYP 方法在6-31G**基组水平上对3种化合物的构型进行了全优化，计算了 Wiberg 键级、键离解能（BDE）和静电势参数、理论密度和固相生成焓，用 Kamlet-Jacobs 公式和最小自由能法计算了爆速、爆压和能量特性。结果表明，DNFP 的键离解能为216．13 kJ/mol，密度为1．903 g/cm3，爆速为8811 m/s，爆压为36．27 GPa，未达到高能量密度化合物的标准；DNFOP 和 DNPTDO 的键离解能分别为80．37和208．59 kJ/mol，密度分别为1．939和1．942 g/cm3，爆速分别为9151和9235 m/s，爆压分别为39．54和40．30 GPa。DNFP、DNFOP 和 DNPT-DO 的理论比冲分别比 RDX 高97．6、120．6和140．6 N·s/kg。