1,3,4,5,7,8-六硝基八氢化二咪唑[4,5-b:4',5'-e]吡嗪-2,6-(1H,3H)-N,N'-二亚硝胺分子结构与性能的量子化学研究

doi:10.7503/cjcu20130858

摘要/Abstract

摘要：

设计了一种新型高能量密度化合物1,3,4,5,7,8-六硝基八氢化二咪唑[4,5-b:4',5'-e]吡嗪-2,6-(1H,3H)-N,N'-二亚硝胺(ONIP). 运用密度泛函理论(DFT), 在B3PW91/6-31G++(d, p)水平下进行优化并计算出了ONIP的一些重要性质. 通过键级的分析, 母环的五元环侧链处N—NO₂键为分解引发键, 其解离能为107.8 kJ/mol; 该化合物理论密度为2.00 g/cm³, 生成热为1693.71 kJ/mol, 爆速为10.21 km/s, 爆压为49.17 GPa, 表明爆轰性能优异; 其撞击感度为33 cm, 优于黑索金(RDX)、奥克托金(HMX)和六硝基六氮杂异伍兹烷(CL-20); 能级差为3.67 eV, 表明分子稳定性较高. 给出了2条合成路线, 均具有步骤少且原料易得的优点.

关键词: 1,3,4,5,7,8-六硝基八氢化二咪唑[4,5-b:4',5'-e]吡嗪-2,6-(1H,3H)-N,N'-二亚硝胺, 高能量密度化合物, 密度泛函理论, 爆轰性能, 感度

Abstract:

A novel high energetic density compound, N,N'-(1,3,4,5,7,8-hexanitrooctahydro-diimidazo[4,5-b:4',5'-e]pyrazine-2,6(1H,3H)-diylidene)dinitramide was designed. The structure and some important properties were optimized and calculated under B3PW91/6-31G++(d,p) level with density functional theory(DFT). By bond order analysis, decomposition was initiated by the rupture of N—NO₂ bond on C atom of imidazole and the bond dissociation enthalpies(BDE) was 107.8 kJ/mol. Then some properties of compounds were calculated. Its density was 2.00 g/cm³, heat of formation was 1693.71 kJ/mol, detonation velocity and pressure were 10.21 km/s and 49.17 GPa, respectively. The stability was also evaluated and proved to be an insensitive energetic material. Its impact sensitivity was 33 cm, which was better than HMX, RDX and CL-20, the energy difference ΔE_(LUMO-HOMO) was 3.67 eV. The results showed that the molecule was stable and NO₂ was the sensitive position. Finally, two possible synthetic routes were also drawn with the advantages of few steps and inexpensive materials.

Key words: N,N'-(1,3,4,5,7,8-hexanitrooctahydrodiimidazo[4,5-b:4',5'-e]pyrazine-2,6(1H,3H)-diylidene)dinitramide, High energy density compound(HEDC), Density functional theory, Explosive property, Sensitivity

中图分类号:

O641

TrendMD:

王鹏程, 陆明. 1,3,4,5,7,8-六硝基八氢化二咪唑[4,5-b:4',5'-e]吡嗪-2,6-(1H,3H)-N,N'-二亚硝胺分子结构与性能的量子化学研究. 高等学校化学学报, 2014, 35(3): 596.

WANG Pengcheng, LU Ming. Computational Study on the Chemical Structure, Explosive Properties and Sensitivity of N,N'-(1,3,4,5,7,8-hexanitrooctahydro-diimidazo [4,5-b:4',5'-e]pyrazine-2,6(1H,3H)-diylidene)dinitramide^†. Chem. J. Chinese Universities, 2014, 35(3): 596.

图/表 8

Fig.1 Molecular structure and atomic numbering of ONIP

Table 1 Bond length and bond order of several typical bonds in ONIP

Bond	Bond length/nm	Bond order	Bond	Bond length/nm	Bond order
C1—N3	0.1471	0.9252	C4＝N15	0.1283	1.7360
N3—C4	0.1415	1.0183	C6—N8	0.1445	0.9702
N3—N19	0.1437	0.9436	N15—N16	0.1466	0.9158
N5—N12	0.1450	0.9227	N8—N9	0.1440	0.9590
C1—H2	0.1090	0.8317	N16—O17	0.1235	1.5570
N9—O10	0.1251	1.4946	N19—O20	0.1246	1.5016

Fig.2 Interaction between the lone pair electrons of N15 and antibonding orbital of C4—N3

Fig.3 Electrostatic potential distribution of ONIP from different directions (A) Top view; (B) side view.

Table 2 Comparison of explosive performance and sensitivity

HEDC	Density/(g·cm^-3)	Velocity/(km·s^-1)	Pressure/GPa	Sensitivity, h₅₀/cm
ONIP	2.00	10.12	49.17	33
HNGG	1.96	9.71	43.96	24
HMX	1.91	9.12	36.16	26
RDX	1.81	8.61	32.71	29
CL-20	2.04	9.46	42.78	14

Fig.4 LUMO and HOMO of ONIP

Fig.5 Density of state(DOS) of ONIPa. TDOS; b. rings; c. groups; d. OPDOS.

Fig.6 Possible synthetic routes of ONIP

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