Skip to main content
SpringerLink
Log in

Theoretical investigation of the effects of the molar ratio and solvent on the formation of the pyrazole–nitroamine cocrystal explosive 3,4-dinitropyrazole (DNP)/2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (CL-20)

  • Original Paper
  • Published:
Journal of Molecular Modeling Aims and scope Submit manuscript

Abstract

The effects of the molar ratio, temperature, and solvent on the formation of the cocrystal explosive DNP/CL-20 were investigated using molecular dynamics (MD) simulation. The cocrystal structure was predicted through Monte Carlo (MC) simulation and using first-principles methods. The results showed that the DNP/CL-20 cocrystal might be more stable in the molar ratio 1:1 near to 318 K, and the most probable cocrystal crystallizes in the triclinic crystal system with the space group P\( \overline{1} \). Cocrystallization was more likely to occur in methanol and ethanol at 308 K as a result of solvent effects. The optimized structure and the reduced density gradient (RDG) of the DNP/CL-20 complex confirmed that the main driving forces for cocrystallization were a series of hydrogen bonds and van der Waals forces. Analyses of the trigger bonds, the charges on the nitro groups, the electrostatic surface potential (ESP), and the free space per molecule in the cocrystal lattice were carried out to further explore their influences on the sensitivity of CL-20. The results indicated that the DNP/CL-20 complex tended to be more stable and insensitive than pure CL-20. Moreover, an investigation of the detonation performance of the DNP/CL-20 cocrystal indicated that it possesses high power.

DNP/CL-20 cocrystal models with different molar ratios were investigated at different temperatures using molecular dynamics (MD) simulation methods. Binding energies and mechanical properties were probed to determine the stability and performance of each cocrystal model. Solvated DNP/CL-20 models were established by adding solvent molecules to the cocrystal surface. The binding energies of the models in various solvents were calculated in order to identify the most suitable solvent and temperature for preparing the cocrystal explosive DNP/CL-20

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4a–c
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Anslyn EV, Dougherty DA (2004) Modern physical organic chemistry. University Science Books, Sausalito

  2. Lara-Ochoa F, Espinosa-Pérez G (2007) Cocrystals definitions. Supramol Chem 19:553–557

    Article  CAS  Google Scholar 

  3. Bolton O, Matzger AJ (2011) Improved stability and smart-material functionality realized in an energetic cocrystal. Angew Chem Int Ed 50:8960–8963

    Article  CAS  Google Scholar 

  4. Lin H, Zhu S-G, Li H-Z, Peng X-H (2013) Structure and detonation performance of a novel HMX/LLM-105 cocrystal explosive. J Phys Org Chem 26:898–907

    Article  CAS  Google Scholar 

  5. Millar DIA, Maynard-Casely HE, Allan DR, Cumming AS, Lennie AR, Mackay AJ, Oswald IDH, Tang C-C, Pulham CR (2012) Crystal engineering of energetic materials: co-crystals of CL-20. Cryst Eng Comm 14:3742–3749

    Article  CAS  Google Scholar 

  6. Yang Z-W, Li H-Z, Huang H, Zhou X-Q, Li J-S, Nie F-D (2013) Preparation and performance of a HNIW/TNT cocrystal explosive. Propell Explos Pyrot 38:495–501

    Article  CAS  Google Scholar 

  7. Bolton O, Simke LR, Pagoria PF, Matzger AJ (2012) High power explosive with good sensitivity: a 2:1 cocrystal of CL-20:HMX. Cryst Growth Des 12:4311–4314

  8. Yang Z-W, Li H-Z, Zhou X-Q, Zhang C-Y, Huang H, Li J-S, Nie F-D (2012) Characterization and properties of a novel energetic–energetic cocrystal explosive composed of HNIW and BTF. Cryst Growth Des 12:5155–5158

  9. Wang Y-P, Yang Z-W, Li H-Z, Zhou X-Q, Zhang Q, Wang J-H, Liu Y-C (2014) A novel cocrystal explosive of HNIW with good comprehensive properties. Propell Explos Pyrot 39:590–596

    Article  CAS  Google Scholar 

  10. Goncharov TK, Aliev ZG, Aldoshin SM, Dashko DV, Vasil AA, Shishov NI, Milekhin YM (2015) Preparation, structure, and main properties of bimolecular crystals CL-20-DNP and CL-20-DNG. Russ Chem B+ 64:366–374

    Article  CAS  Google Scholar 

  11. Xu H-F, Duan X-H, Li H-Z, Pei C-H (2015) A novel high-energetic and good-sensitive cocrystal composed of CL-20 and TATB by a rapid solvent/non-solvent method. RSC Adv. 5:95764–95770

    Article  CAS  Google Scholar 

  12. Liu K, Zhang G, Luan J-Y, Chen Z-Q, Su P-F, Shu Y-J (2016) Crystal structure, spectrum character and explosive property of a new cocrystal CL-20/DNT. J Mol Struct 1110:91–96

    Article  CAS  Google Scholar 

  13. Gao H, Jiang W, Liu J, Hao G-Z, Xiao L, Ke X, Chen T (2017) Synthesis and characterization of a new co-crystal explosive with high energy and good sensitivity. J Energ Mater 35:490–498

  14. Ding X, Gou R-J, Ren F-D, Liu F, Zhang S-H, Gao H-F (2016) Molecular dynamics simulation and density functional theory insight into the cocrystal explosive of hexaazaisowurtzitane/nitroguanidine. Int J Quantum Chem 116:88–96

    Article  CAS  Google Scholar 

  15. Gao H-F, Zhang S-H, Ren F-D, Liu F, Gou R-J, Ding X (2015) Theoretical insight into the co-crystal explosive of 2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (CL-20)/1,1-diamino-2,2-dinitroethylene (FOX-7). Comput Mater Sci 107:33–41

    Article  CAS  Google Scholar 

  16. Feng R-Z, Zhang S-H, Ren F-D, Gou R-J, Gao L (2016) Theoretical insight into the binding energy and detonation performance of ε-, γ-, β-CL-20 cocrystals with β-HMX, FOX-7, and DMF in different molar ratios, as well as electrostatic potential. J Mol Model 22:1–14

    Article  Google Scholar 

  17. Wei X-F, Zhang A-B, Ma Y, Xue X-G, Zhou J-H, Zhu Y-Q, Zhang C-Y (2015) Toward low-sensitive and high-energetic cocrystal III: thermodynamics of energetic–energetic cocrystal formation. Cryst Eng Comm 17:9037–9047

    Article  CAS  Google Scholar 

  18. Gao H-F, Zhang S-H, Ren F-D, Gou R-J, Wu C-L (2016) Theoretical insight into the temperature-dependent acetonitrile (ACN) solvent effect on the diacetone diperoxide (DADP)/1,3,5-tribromo-2,4,6-trinitrobenzene (TBTNB) cocrystallization. Comput Mater Sci 121:232–239

  19. Han G, Gou R-J, Ren F-D, Zhang S-H, Zhu S-F (2017) Theoretical investigation into the influence of molar ratio on binding energy, mechanical property and detonation performance of 1,3,5,7-tetranitro 1,3,5,7-tetrazacyclo octane (HMX)/1-methyl-4,5-dinitroimidazole (MDNI) cocrystal explosive. Comput Theor Chem 1109:27–35

    Article  CAS  Google Scholar 

  20. Ravi P, Badgujar DM, Gore GM, Tewari SP, Sikder AK (2011) Review on melt cast explosive. Prop Explos Pyrotech 36:393–403

    Article  CAS  Google Scholar 

  21. Nielsen AT, Christian SL, Moore DW, Nadler MP, Nissan RA, Vanderah DJ, Gilardi RD, George CF, Flippen-Anderson JL, Chafin AP (1998) Synthesis of polyazapolycyclic caged polynitramines. Tetrahedron 54:11793–11812

    Article  CAS  Google Scholar 

  22. Chen L-Z, Song L, Cao D-L, Wang J-L (2016) Crystal structure of 3,4-dinitropyrazole, C3H2N4O4. Z Kristallogr—New Cryst Struct 231:1099–1100

  23. Sun H (1998) COMPASS: an ab initio force-field optimized for condensed-phase applications—overview with details on alkane and benzene compounds. J Phys Chem B 102:7338–7364

  24. Wei C-X, Huang H, Duan X-H, Pei C-H (2011) Structures and properties prediction of HMX/TATB co-crystal. Propell Explos Pyrot 36:416–423

    Article  CAS  Google Scholar 

  25. Li Y-X, Chen S-S, Ren F-D (2015) Theoretical insights into the structures and mechanical properties of HMX/NQ cocrystal explosives and their complexes, and the influence of molecular ratios on their bonding energies. J Mol Model 21:245

    Article  CAS  Google Scholar 

  26. Andersen HC (1980) Molecular dynamics simulations at constant pressure and/or temperature. J Chem Phys 72:2384–2393

    Article  CAS  Google Scholar 

  27. Allan DR, Clark SJ, Brugmans MJP, Ackland GJ, Vos WL (1998) Structure of crystalline methanol at high pressure. Phys Rev B 58:R11809

    Article  CAS  Google Scholar 

  28. Accelrys Software Inc. (2013) Materials Studio release notes, release 7.0. Accelrys Software Inc., San Diego

  29. Becke AD (1993) Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648–5652

    Article  CAS  Google Scholar 

  30. Zhao Y, Truhlar DG (2008) The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor Chim Acta 120:215–241

    Article  CAS  Google Scholar 

  31. Grimme S (2006) Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J Comput Chem 27:1787–1799

    Article  CAS  Google Scholar 

  32. Boys SF, Bernardi F (1970) The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors. Mol Phys 19:553–566

    Article  CAS  Google Scholar 

  33. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery Jr JA, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09, revision A.01. Gaussian, Inc., Wallingford

  34. Lu T, Chen FW (2012) Multiwfn: A multifunctional wavefunction analyzer. J Comput Chem 33:580–592

    Article  Google Scholar 

  35. Bondi A (1964) van der Waals volumes and radii. J Phys Chem 68:441–451

    Article  CAS  Google Scholar 

  36. Razas I (2007) On the nature of hydrogen bonds: an overview on computational studies and a word about patterns. Phys Chem Chem Phys 9:2782–2790

    Article  Google Scholar 

  37. Arunan E, Desiraju GR, Klein RA, Sadlej J, Scheiner S, Alkorta I, Clary DC, Crabtree RH, Dannenberg JJ, Hobza P, Kjaergaard HG, Legon AC, Mennucci B, Nesbitt DJ (2011) Definition of the hydrogen bond (IUPAC recommendations 2011). Pure Appl Chem 83:1637–1641

    CAS  Google Scholar 

  38. Barckholtz C, Barckholtz TA, Hadad CM (1999) C−H and N−H bond dissociation energies of small aromatic hydrocarbons. J Am Chem Soc 121:491–500

    Article  CAS  Google Scholar 

  39. Lu T, Chen F-W (2013) Bond order analysis based on the Laplacian of electron density in fuzzy overlap space. J Phys Chem A 117:3100–3108

    Article  CAS  Google Scholar 

  40. Rice BM, Hare JJ (2002) A quantum mechanical investigation of the relation between impact sensitivity and the charge distribution in energetic molecules. J Phys Chem A 106:1770–1783

    Article  CAS  Google Scholar 

  41. Lu T, Chen F-W (2012) Atomic dipole moment corrected Hirshfeld population method. Theor Comput Chem 11:163–183

  42. Steiner T (2002) The hydrogen bond in the solid state. Angew Chem Int Ed 41:48–76

    Article  CAS  Google Scholar 

  43. Johnson ER, Keinan S, Mori-Sanchez P, Contreras-Garcia J, Cohen AJ, Yang W-T (2010) Revealing noncovalent interactions. J Am Chem Soc 132:6498–6506

    Article  CAS  Google Scholar 

  44. Bader RFW (1991) A quantum theory of molecular structure and its applications. Chem Rev 91:893–928

    Article  CAS  Google Scholar 

  45. Pospíšil M, Vávra P, Concha MC, Murray JS, Politzer P (2010) A possible crystal volume factor in the impact sensitivities of some energetic compounds. J Mol Model 16:895–901

    Article  Google Scholar 

  46. Politzer P, Murray JS (2016) High performance, low sensitivity: conflicting or compatible? Propell Explos Pyrot 41:414–425

    Article  CAS  Google Scholar 

  47. Lin H, Zhu S-G, Zhang L, Peng X-H, Chen P-Y, Li H-Z (2013) Intermolecular interactions, thermodynamic properties, crystal structure, and detonation performance of HMX/NTO cocrystal explosive. Int J Quantum Chem 113:1591–1599

    Article  CAS  Google Scholar 

  48. Landenberger KB, Matzger AJ (2010) Cocrystal engineering of a prototype energetic material: supramolecular chemistry of 2,4,6-trinitrotoluene. Cryst Growth Des 10:5341–5347

  49. Politzer P, Murray JS (2015) Some molecular/crystalline factors that affect the sensitivities of energetic materials: molecular surface electrostatic potentials, lattice free space and maximum heat of detonation per unit volume. J Mol Model 21:25–35

    Article  Google Scholar 

  50. Politzer P, Murray JS (2014) Detonation performance and sensitivity: a quest for balance. Adv Quantum Chem 69:1–30

  51. Pospíšil M, Vávra P, Concha MC, Murray JS, Politzer P (2011) Sensitivity and the available free space per molecule in the unit cell. J Mol Model 17:2569–2574

    Article  Google Scholar 

  52. Politzer P, Murray JS (2014) Impact sensitivity and crystal lattice compressibility/free space. J Mol Model 20:2223–2230

    Article  Google Scholar 

  53. Marenich AV, Cramer CJ, Truhlar DG (2009) Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. J Phys Chem B 113:6378–6396

    Article  CAS  Google Scholar 

  54. Wu J-T, Zhang J-G, Li T, Li Z-M, Zhang T-L (2015) A novel cocrystal explosive NTO/TZTN with good comprehensive properties. RSC Adv 5:28354–28359

    Article  CAS  Google Scholar 

  55. Wei Y-J, Ren F-D, Shi W-J, Zhao Q (2016) Theoretical insight into the influences of molecular ratios on stabilities and mechanical properties, solvent effect of HMX/FOX-7 cocrystal explosive. J Energ Mater 34:426–439

    Article  CAS  Google Scholar 

  56. Sućeska M (2013) EXPLO5 6.0.1. Brodarski Institute, Zagreb

  57. Keshavarz MH, Motamedoshariati H, Moghayadnia R, Nazari HR, Azarniamehraban J (2009) A new computer code to evaluate detonation performance of high explosives and their thermochemical properties, part I. J Hazard Mater 172:1218–1228

    Article  CAS  Google Scholar 

  58. Politzer P, Murray JS (2015) Impact sensitivity and the maximum heat of detonation. J Mol Model 21:262–272

    Article  Google Scholar 

Download references

Acknowledgments

We gratefully acknowledge the National Key Laboratory of Applied Physics and Chemistry for financial support.

Author information

Authors and Affiliations

  1. School of Chemical and Environmental Engineering, North University of China, Taiyuan, Shanxi, 030051, China

    Shuang-fei Zhu, Shu-hai Zhang, Rui-jun Gou, Gang Han, Chun-lei Wu & Fu-de Ren

  2. National Key Laboratory of Applied Physics and Chemistry, Xi’an, Shanxi, 710061, China

    Shuang-fei Zhu

Authors
  1. Shuang-fei Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Shu-hai Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Rui-jun Gou
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Gang Han
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Chun-lei Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Fu-de Ren
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Shu-hai Zhang.

Electronic supplementary material

ESM 1

(DOCX 1458 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhu, Sf., Zhang, Sh., Gou, Rj. et al. Theoretical investigation of the effects of the molar ratio and solvent on the formation of the pyrazole–nitroamine cocrystal explosive 3,4-dinitropyrazole (DNP)/2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (CL-20). J Mol Model 23, 353 (2017). https://doi.org/10.1007/s00894-017-3516-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00894-017-3516-4

Keywords

Search

Navigation