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†

doi:10.7503/cjcu20130858

Abstract

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

CLC Number:

O641

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2014, 35(3): 596.

Figures/Tables 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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