First-Principles Study on Structural, Electronic and Optical Properties of G2ZT Crystal under High Pressure
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摘要: 基于密度泛函理论的第一性原理研究了高压下富氮含能材料（双3, 4, 5-三氨基-1, 2, 4-三唑）-5, 5′-偶氮四唑（G2ZT）的几何结构、电子结构和光学性质。结果表明，在考虑范德瓦尔斯色散修正和密度泛函色散修正的情况下, 分子晶体结构数据与实验结果的相对误差均在3%以内。Hirshfeld表面分析结果表明，随着压强增大，分子间氢键的相互作用减弱。G2ZT晶体在零压下的能带带隙为2.03 eV，是一种p型半导体。随着压强增大，带隙变窄，吸收系数可达到3.0×106 cm−1。研究结果为进一步分析高压下G2ZT晶体的特征提供了理论参考。Abstract: Geometric structure, electronic structure and optical properties of nitrogen-rich energetic materials (bis 3, 4, 5-triamino-1, 2, 4-triazole)-5, 5′-azotetrazole (G2ZT) at high pressures are investigated using first-principles based on density functional theory. The calculated results obtained by using vdW-DF2 and PBE-D2 methods show that the crystal structure data fit well with the experimental results, and the error rates are all within 3%. Hirshfeld surface analyses indicate that interactions of the inter-molecular hydrogen bond are weaken with the increasing pressure. G2ZT crystal possesses a band gap of 2.03 eV at zero pressure, and it is a p-type semiconductor. As the pressure increases, the band gap becomes narrower and the absorption coefficient can approach 3.0×106 cm−1. These results provide a theoretical reference for further analysis of G2ZT crystal’s characteristics under high pressure.
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Key words:
- G2ZT crystal /
- high pressure /
- electronic structure /
- optical properties
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图 2 G2ZT晶体的晶格参数和体积比随压强的变化
Figure 2. Lattice parameters and V/V0 of G2ZT crystal versus pressure
图 3 C2N10分子在0 GPa下的Hirshfeld面和二维指纹图
Figure 3. Hirshfeld surface and two-dimensional finger patterns of C2N10 molecule at 0 GPa
图 4 C2N10分子在40 GPa下的Hirshfeld面和二维指纹图
Figure 4. Hirshfeld surface and two-dimensional finger patterns of C2N10 molecule at 40 GPa
图 5 G2ZT晶体在不同压强下的能带色散关系
Figure 5. Energy band dispersion of G2ZT crystal at different pressures
图 6 不同压强下G2ZT晶体的态密度分布
Figure 6. Distributions of DOS of G2ZT crystal at different pressures
图 7 不同压强下G2ZT晶体的介电函数随入射能量的变化
Figure 7. Dielectric functions of G2ZT crystal versus incident energy at different pressures
图 8 G2ZT晶体在0和40 GPa压强下的反射率随入射能量的变化
Figure 8. Reflection index of G2ZT crystal versus incident energy at 0 and 40 GPa
图 9 G2ZT晶体在0和40 GPa压强下的折射率随入射能量的变化
Figure 9. Refraction index of G2ZT crystal versus incident energy at 0 and 40 GPa
图 10 G2ZT晶体在0和40 GPa压强下的吸收系数随入射能量的变化
Figure 10. Absorption coefficient of G2ZT crystal versus incident energy at 0 and 40 GPa
表 1 G2ZT晶格参数的计算结果和实验结果比较[2]
Table 1. Calculated crystal lattice parameters of G2ZT compared with experimental data[2]
Method a/Å b/Å c/Å $\alpha $/(°) $\,\beta $/(°) $\gamma $/(°) V/Å3 vdW-DF2 5.3733 6.6044 11.9931 102.36 91.14 109.42 390.1694 PBE-D2 5.3540 6.7920 11.7190 100.23 91.80 110.55 390.6893 Expt.[2] 5.2619 6.6980 11.8840 102.05 90.80 109.96 383.3499 $\delta $vdW-DF2/% 2.10 −1.40 0.92 0.30 0.37 −0.49 1.80 $\delta $PBE-D2/% 1.70 1.40 −1.40 −1.80 1.10 0.53 1.90 
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表 2 三阶BM和Vinet物态方程拟合得到的G2ZT晶体的体弹模量及其一阶导数
Table 2. Bulk moduli and their pressure-derivatives of G2ZT crystal determined by third-order BM and Vinet equations of state
Method Third-order BM Vinet B0/GPa $B_0' $ B0/GPa $B_0' $ PBE-D2 19.69±0.80 5.50±0.22 18.84±0.63 6.06±0.16 vdW-DF2 27.58±0.76 4.85±0.14 26.48±0.66 5.39±0.13
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表 3 不同压强下第一布里渊区高对称
$k$ 点在价带顶$E_{\rm{v}}$ 和导带底$E_{\rm{c}} $ 的特征能量Table 3. Characteristic energy values for top of valence band
$E_{\rm{v}} $ and bottom of conduction band$E_{\rm{c}} $ in highly symmetric$k$ points of the first Brillouin region at different pressuresPressure/GPa Ec/eV Ev/eV R Γ X M R Γ X M 0 2.03 2.25 2.03 2.03 0.00 −0.05 0.00 0.00 3 1.73 2.01 1.73 1.73 0.00 −0.04 0.00 0.00 10 1.33 1.66 1.31 1.33 0.00 −0.09 −0.03 0.00 40 0.93 1.46 0.81 0.91 −0.04 −0.25 −0.18 0.00
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[1] KLAPÖTKE T M, SABATÉ C M. Bistetrazoles: nitrogen-rich, high-performing, insensitive energetic compounds [J]. Chemistry of Materials, 2008, 20(11): 3629–3637. doi: 10.1021/cm703657k [2] KLAPÖTKE T M, SABATÉ C M. 5, 5′-Hydrazinebistetrazole: an oxidation-stable nitrogen-rich compound and starting material for the synthesis of 5, 5′-Azobistetrazolates [J]. Zeitschrift für Anorganische und Allgemeine Chemie, 2007, 633(15): 2671–2677. [3] KARAGHIOSOFF K, KLAPÖTKE T M, SABATÉ C M. Nitrogen-rich compounds in pyrotechnics: alkaline earth metal salts of 5, 5′-hydrazine-1, 2-diylbis (1H-tetrazole) [J]. European Journal of Inorganic Chemistry, 2009(2): 238–250. doi: 10.1002/ejic.200800939 [4] EBESPÄCHER M, KLAPÖTKE T M, SABATÉ C M. Nitrogen-rich alkali metal 5, 5′-hydrazinebistetrazolate salts: environmentally friendly compounds in pyrotechnic mixtures [J]. New Journal of Chemistry, 2009, 33(3): 517–527. doi: 10.1039/B818927G [5] DE LUCIA F C JR, GOTTFRIED J L. Characterization of a series of nitrogen-rich molecules using laser induced breakdown spectroscopy [J]. Propellants, Explosives, Pyrotechnics, 2010, 35(3): 268–277. doi: 10.1002/prep.201000009 [6] DREGER Z A, STASH A I, YU Z G, et al. High-pressure structural response of an insensitive energetic crystal: dihydroxylammonium 5, 5′-bistetrazole-1, 1′-diolate (TKX-50) [J]. The Journal of Physical Chemistry C, 2017, 121(10): 5761–5767. doi: 10.1021/acs.jpcc.7b00867 [7] FANG X, STONE M, STENNETT C. Pulsed laser irradiation of a nanoparticles sensitized RDX crystal [J]. Combustion and Flame, 2020, 214: 387–393. doi: 10.1016/j.combustflame.2020.01.009 [8] ISBELL R A, BREWSTER M Q. Optical properties of energetic materials: RDX, HMX, AP, NC/NG, and HTPB [J]. Propellants, Explosives, Pyrotechnics, 1998, 23(4): 218–224. doi: 10.1002/(SICI)1521-4087(199808)23:4<218::AID-PREP218>3.0.CO;2-A [9] ORDEJÓN P, ARTACHO E, SOLER J M. Self-consistent order-N density-functional calculations for very large systems [J]. Physical Review B, 1996, 53(16): R10441–R10444. doi: 10.1103/PhysRevB.53.R10441 [10] SÁNCHEZ-PORTAL D, ORDEJÓN P, ARTACHO E, et al. Density-functional method for very large systems with LCAO basis sets [J]. International Journal of Quantum Chemistry, 1997, 65(5): 453–461. doi: 10.1002/(SICI)1097-461X(1997)65:5<453::AID-QUA9>3.0.CO;2-V [11] SOLER J M, ARTACHO E, GALE J D, et al. The SIESTA method for ab initio order-N materials simulation [J]. Journal of Physics: Condensed Matter, 2002, 14(11): 2745–2779. doi: 10.1088/0953-8984/14/11/302 [12] DION M, RYDBERG H, SCHRÖDER E, et al. Van der Waals density functional for general geometries [J]. Physical Review Letters, 2004, 92(24): 246401. doi: 10.1103/PhysRevLett.92.246401 [13] HAMADA I. Van der Waals density functional made accurate [J]. Physical Review B, 2014, 89(12): 121103. doi: 10.1103/PhysRevB.89.121103 [14] GRIMME S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction [J]. Journal of Computational Chemistry, 2006, 27(15): 1787–1799. doi: 10.1002/jcc.20495 [15] GRIMME S, EHRLICH S, GOERIGK L. Effect of the damping function in dispersion corrected density functional theory [J]. Journal of Computational Chemistry, 2011, 32(7): 1456–1465. doi: 10.1002/jcc.21759 [16] TROULLIER N, MARTINS J L. Efficient pseudopotentials for plane-wave calculations [J]. Physical Review B, 1991, 43(3): 1993–2006. doi: 10.1103/PhysRevB.43.1993 [17] SANKEY O F, NIKLEWSKI D J. Ab initio multicenter tight-binding model for molecular dynamics simulations and other applications in covalent systems [J]. Physical Review B, 1989, 40(6): 3979–3995. doi: 10.1103/PhysRevB.40.3979 [18] JUNQUERA J, PAZ Ó, SÁNCHEZ-PORTAL D, et al. Numerical atomic orbitals for linear-scaling calculations [J]. Physical Review B, 2001, 64(23): 235111. doi: 10.1103/PhysRevB.64.235111 [19] MONKHORST H J, PACK J D. Special points for Brillouin-zone integrations [J]. Physical Review B, 1976, 13(12): 5188–5192. doi: 10.1103/PhysRevB.13.5188 [20] TRAN F, BLAHA P. Accurate band gaps of semiconductors and insulators with a semilocal exchange-correlation potential [J]. Physical Review Letters, 2009, 102(22): 226401. doi: 10.1103/PhysRevLett.102.226401 [21] AMBROSCH-DRAXL C, SOFO J O. Linear optical properties of solids within the full-potential linearized augmented planewave method [J]. Computer Physics Communications, 2006, 175(1): 1–14. doi: 10.1016/j.cpc.2006.03.005 [22] TOLL J S. Causality and the dispersion relation: logical foundations [J]. Physical Review, 1956, 104(6): 1760–1770. doi: 10.1103/PhysRev.104.1760 [23] RIVAS-SILVA J F, BLAS M A, HOAT D M. Theoretical study of electronic and optical properties of antiferromagnetic β-MnS using the modified becke johnson (mBJ) potential [J]. Journal of Physics and Chemistry of Solids, 2017, 128: 310–315. [24] BIRCH F. Finite elastic strain of cubic crystals [J]. Physical Review, 1947, 71(11): 809–824. doi: 10.1103/PhysRev.71.809 [25] VINET P, FERRANTE J, SMITH J R, et al. A universal equation of state for solids [J]. Journal of Physics C: Solid State Physics, 1986, 19(20): L467–L473. doi: 10.1088/0022-3719/19/20/001 [26] MCKINNON J J, JAYATILAKA D, SPACKMAN M A. Towards quantitative analysis of intermolecular interactions with Hirshfeld surfaces [J]. Chemistry Communications, 2007(37): 3814–3816. doi: 10.1039/b704980c [27] SPACKMAN M A, JAYATILAKA D. Hirshfeld surface analysis [J]. CrystEngComm, 2009, 11(1): 19–32. doi: 10.1039/B818330A [28] SPACKMAN P R, TURNER M J, MCKINNON J J, et al. CrystalExplorer: a program for Hirshfeld surface analysis, visualization and quantitative analysis of molecular crystals [J]. Journal of Applied Crystallography, 2021, 54(3): 1006–1011. doi: 10.1107/S1600576721002910 -
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