Periodic DFT Study on Structural Transformations of Crystalline Hydrazinium 5-Nitramino-3,4-dinitropyrazolate Under High Pressures†

doi:10.7503/cjcu20170465

Abstract

Abstract:

Periodic density functional theory(DFT) calculations were performed to study the crystal, molecular and electronic structures of energetic hydrazinium 5-nitramino-3,4-dinitropyrazolate(HNDP) in the pressure range of 0—160 GPa. The results indicate that crystalline HNDP undergoes three structural transformations. The first one occurs at 6 GPa with the rearrangement of the molecules in the crystal and the rupture of the N17—H23…N13 hydrogen bond. At 28 GPa, the second one forms N17—H23…N13 hydrogen bond again. The last one occurs at 110 GPa with the rupture of the N17—H19 covalent bond and N20—H22…O24 hydrogen bond. An analysis of band gaps, bond populations and atomic charges show that HNDP crystal undergoes an electronic transition to the metallic system with the increase in pressure. These results provide basic information for the high pressure behavior of crystalline HNDP.

Key words: Density functional theory, Hydrazinium 5-nitramino-3, 4-dinitropyrazolate(HNDP), High pressure, Crystalline structure

CLC Number:

O641

TrendMD:

ZHAO Guozheng, FAN Rongrong, YAN Xilin, TANG Wei, TANG Mingfeng, JIA Jianfeng, WU Haishun. Periodic DFT Study on Structural Transformations of Crystalline Hydrazinium 5-Nitramino-3,4-dinitropyrazolate Under High Pressures^†[J]. Chem. J. Chinese Universities, 2018, 39(2): 292.

Figures/Tables 11

Fig.1 Crystal(A) and molecular structures(B) of HNDP

Table 1 Comparison of relaxed lattice parameters of HNDP with experimental data at ambient conditions*

Method	a/nm	b/nm	c/nm	β/(°)	Cell volume/nm³
LDA/CA-PZ	0.350(-3.58)	1.064(-0.56)	2.218(-2.33)	92.14(-0.33)	0.825(-6.36)
LDA/CA-PZ-OBS	0.333(-8.26)	1.040(-2.80)	2.161(-4.84)	88.04(-4.77)	0.747(-15.21)
GGA/PBE	0.406(11.85)	1.167(9.07)	2.392(5.33)	97.60(5.57)	1.124(27.58)
GGA/PBE-TS	0.369(1.65)	1.111(3.83)	2.327(2.47)	94.86(2.61)	0.949(7.72)
Exp.	0.363	1.070	2.271	92.45	0.881

Table 2 Experimental and calculated bond lengths and angles for HNDP

Species	d/nm		Species	Bond angle/(°)
Species	LDA/CA-PZ		Exp.	LDA/CA-PZ	Exp.
N6—C2	0.136	0.136	C3—C1—N7	129.32	129.08
C1—C2	0.141	0.140	N5—N6—H4	119.21	123.20
C1—C3	0.140	0.140	N13—C2—C1	126.27	125.86
C3—N5	0.132	0.131	O11—N10—C3	116.37	117.14
N5—N6	0.135	0.136	O15—N14—O16	121.11	119.98

Fig.2 Lattice constants a(A), b(B), c(C) and compression rates(D) of HNDP as a function of pressure

Fig.3 Unit cell volume(A) and total energy(B) at the pressure range of 0—160 GPa

Fig.4 Variation of the bond lengths and interatomic distances of HNDP with different pressure

Fig.5 Variation of the bond angles of HNDP with different pressure

Fig.6 Perspective view of HNDP with different pressures (A) 6 GPa; (B) 28 GPa; (C) 110 GPa.

Fig.7 Bond populations(A) and atomic charges(B) in HNDP at different pressures

Fig.8 Band gaps of HNDP under different pressures

Fig.9 Total DOS of HNDP under different pressuresPressure/Pa: (A) 0; (B) 6; (C) 28; (D) 110. s, p, and total states are shown as dotted, dashed, and solid curves, respectively.

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