Journal of Materials Science

, Volume 55, Issue 1, pp 237–249 | Cite as

First-principle study and Hirshfeld surface analysis on the effect of H2O, NH3 and H2S on structural, electronic, elastic, optical and thermodynamic properties of a novel high-energy crystal 2,4,6-triamino-5-nitropyrimidine-1,3-dioxide

  • Qiong WuEmail author
  • Mingquan Li
  • Qinnan Hu
  • Zewu Zhang
  • Weihua Zhu
Computation & theory


2,4,6-Triamino-5-nitropyrimidine-1,3-dioxide (ICM-102) is a new high-energy crystal which has outstanding combination of performance, effects of three common small molecules H2O, NH3 and H2S on its molecular, crystal and electronic structures, and elastic, optical and thermodynamic properties of the compound were studied by the first-principle calculation and Hirshfeld surface analysis in this work. The results showed that H2O, NH3 and H2S do have significant effects on the structure and property of ICM-102, and different molecules made various influence on all kinds of properties. The low-sensitivity feature of ICM-102 was confirmed, and H2O molecule was found to further increase the stability of ICM-102 crystal obviously by enriching different kinds of close contacts. While the stabilization effect of NH3 and H2S on the ICM-102 was weaker than that of H2O and H2O also improved the density, stiffness, fracture strength and ductility, absorption to purple, blue, green and yellow lights, and thermodynamics parameters of ICM-102, but it decreased the band gap, anisotropy, plasticity, absorption to near ultraviolet and orange, red and infrared lights, and dielectric constant. However, different to H2O, NH3 and H2S reduced stiffness, fracture strength and ductility but increased the band gap of ICM-102. Besides, H2S was found to completely eliminate the region where light cannot be transmitted in the solid crystal ICM-102. This study may be helpful for using small molecules to stabilize the structure and adjust the property of energetic materials.



The present work was supported by the Natural Science Foundation of Jiangsu (BK20170761, BK20160774), the Natural Science Foundation of Nanjing Institute of Technology (JCYJ201806, CKJA201603), the Jiangsu Key Laboratory Opening Project of Advanced Structural Materials and Application Technology (ASMA201707), Outstanding Scientific and Technological Innovation Team in Colleges and Universities of Jiangsu Province, and Jiangsu Overseas Visiting Scholar Program for University Prominent Young and Middle-aged Teachers and Presidents.

Compliance with ethical standards

Conflict of interest

The authors declare no conflicts of interest.


  1. 1.
    Wang Y, Liu Y, Song S, Yang Z, Qi X, Wang K, Liu Y, Zhang Q, Tian Y (2018) Accelerating the discovery of insensitive high-energy-density materials by a materials genome approach. Nat Commun 9:2444CrossRefGoogle Scholar
  2. 2.
    Xu Y, Wang Q, Shen C, Lin Q, Wang P, Lu M (2017) A series of energetic metal pentazolate hydrates. Nature 549:78–81CrossRefGoogle Scholar
  3. 3.
    Zhang C, Sun C, Hu B, Yu C, Lu M (2017) Synthesis and characterization of the pentazolate anion cyclo-N5 in (N5)6(H3O)3(NH4)4Cl. Science 355(6323):374–376CrossRefGoogle Scholar
  4. 4.
    Xu Y, Lin Q, Wang P, Lu M (2018) Syntheses, crystal structures and properties of a series of 3D metal-inorganic frameworks containing pentazolate anion. Chem-Asian J 13(13):1669–1673CrossRefGoogle Scholar
  5. 5.
    Xu Y, Tian L, Wang P, Lin Q, Lu M (2019) Hydrogen bonding network: stabilization of the pentazolate anion in two nonmetallic energetic salts. Cryst Growth Des 19(3):1853–1859CrossRefGoogle Scholar
  6. 6.
    Tappan BC, Brill TB (2003) Thermal decomposition of energetic materials 86 cryogel synthesis of nanocrystalline CL-20 coated with cured nitrocellulose. Propellants Explos Pyrotech 28(5):223–230CrossRefGoogle Scholar
  7. 7.
    Ding Z, Cao W, Ma X, Hang X, Zhang Y, Xu K, Huang J (2019) Synthesis, structure analysis and thermal behavior of two new complexes: Cu(NH3)4(AFT)2 and Cu(C3H6N2H4)2(AFT)2. J Mol Struct 1175:373–378CrossRefGoogle Scholar
  8. 8.
    Bogusz R, Rećko J, Magnuszewska P, Lewczuk R (2018) Application of the energetic complex [Cu(TNBI)(NH3)2(H2O)] in heterogeneous solid rocket propellants. Cent Eur J Energ Mater 15(2):391–402CrossRefGoogle Scholar
  9. 9.
    Wu BD, Yang L, Wang SW, Zhang TL, Zhang JG, Zhou ZN, Yu KB (2011) Preparation, crystal structure, thermal decomposition, and explosive properties of a novel energetic compound [Zn(N2H4)2(N3)2]n: a new high-nitrogen material (N = 65.60%). Z Anorg Allg Chem 637(3–4):450–455CrossRefGoogle Scholar
  10. 10.
    Liu Z, Zhang T, Zhang J, Wang S (2008) Studies on three-dimensional coordination polymer [Cd2(N2H4)2(N3)4]n: crystal structure, thermal decomposition mechanism and explosive properties. J Hazard Mater 154(1–3):832–838CrossRefGoogle Scholar
  11. 11.
    Luo JH, Chen LY, Nguyen DN, Guo D, An Q, Cheng MJ (2018) Dual functions of water in stabilizing metal-pentazolate hydrates [M(N5)2(H2O)4]·4H2O (M = Mn, Fe Co, and Zn) high-energy-density materials. J Phys Chem C 122(37):21192–21201CrossRefGoogle Scholar
  12. 12.
    Zhang L, Chen L, Wang C, Wu JY (2013) Molecular dynamics study of the effect of H2O on the thermal decomposition of α Phase CL-20. Acta Phys-Chim Sin 29(6):1145–1153Google Scholar
  13. 13.
    Clark SJ, Segall MD, Pickard CJ, Hasnip PJ, Probert MI, Refson K, Payne MC (2005) First principles methods using CASTEP. Z Kristallogr 220:567–570Google Scholar
  14. 14.
    Hamann DR, Schlüter M, Chiang C (1979) Norm-conserving pseudopotentials. Phys Rev Lett 43(20):1494CrossRefGoogle Scholar
  15. 15.
    Tkatchenko A, Scheffler M (2009) Accurate molecular van der Waals interactions from ground-state electron density and free-atom reference data. Phys Rev Lett 102(7):073005CrossRefGoogle Scholar
  16. 16.
    Grimme S (2006) Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J Comput Chem 27(15):1787–1799CrossRefGoogle Scholar
  17. 17.
    Fischer TH, Almlof J (1992) General methods for geometry and wave function optimization. J Phys Chem 96(24):9768–9774CrossRefGoogle Scholar
  18. 18.
    Wolff S, Grimwood D, McKinnon J, Turner M, Jayatilaka D, Spackman M (2012) Crystalexplorer (version 3.0). University of Western Australia, CrawleyGoogle Scholar
  19. 19.
    Zhang W, Zhang J, Deng M, Qi X, Nie F, Zhang Q (2017) A promising high-energy-density material. Nat Commun 8:181CrossRefGoogle Scholar
  20. 20.
    Tian B, Xiong Y, Chen L, Zhang C (2018) Relationship between the crystal packing and impact sensitivity of energetic materials. CrystEngComm 20(6):837–848CrossRefGoogle Scholar
  21. 21.
    Ma Y, Meng L, Li H, Zhang C (2017) Enhancing intermolecular interactions and their anisotropy to build low-impact-sensitivity energetic crystals. CrystEngComm 19(23):3145–3155CrossRefGoogle Scholar
  22. 22.
    Spackman MA, McKinnon JJ (2002) Fingerprinting intermolecular interactions in molecular crystals. CrystEngComm 4(66):378–392CrossRefGoogle Scholar
  23. 23.
    Born M, Huang K (1982) Dynamical Theory and Experiment I. Springer-Verlag, BerlinGoogle Scholar
  24. 24.
    Davidson AJ, Dias RP, Dattelbaum DM, Yoo CS (2011) “Stubborn” triaminotrinitrobenzene: unusually high chemical stability of a molecular solid to 150 GPa. J Chem Phys 135(17):174507CrossRefGoogle Scholar
  25. 25.
    Pugh SF (1954) XCII. Relations between the elastic moduli and the plastic properties of polycrystalline pure metals. Philos Mag 45(367):823–843CrossRefGoogle Scholar
  26. 26.
    Saha S, Sinha TP (2000) Electronic structure, chemical bonding, and optical properties of paraelectric BaTiO3. Phys Rev B 62(13):8828CrossRefGoogle Scholar
  27. 27.
    Zhu W, Xiao J, Xiao H (2006) Comparative first-principles study of structural and optical properties of alkali metal azides. J Phys Chem B 110(20):9856–9862CrossRefGoogle Scholar

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Authors and Affiliations

  1. 1.School of Materials Science and EngineeringNanjing Institute of TechnologyNanjingChina
  2. 2.Jiangsu Key Laboratory of Advanced Structural Materials and Application TechnologyNanjingChina
  3. 3.Institute for Computation in Molecular and Materials Science and Department of ChemistryNanjing University of Science and TechnologyNanjingChina

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