Skip to main content
SpringerLink
Log in

Design of insensitive high explosives based on FOX-7: a theoretical prospectives

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

Abstract

Context

This article presents a theoretical study of three insensitive high explosives based on the FOX-7 moiety. A few heterocyclic five- and six-member nitrogen-rich compounds have been created in an effort to better serve as a potential insensitive high explosive. It has been addressed how these molecules should be optimised in terms of stability, sensitivity, detonation properties, IR frequency computations, formal charge calculations, and more. Comprehensive research has been done on these compounds’ molecular density and energy of activation associated with the conversion from nitro (C-NO2) to nitrito (C-ONO) during the initial phase of their decomposition. The bond dissociation energy along with BSSE correction for the most reactive C-NO2 bond is examined. The two designed molecules have intra-molecular hydrogen-bonding while other does not have any intra-molecular hydrogen-bonding. The newly designed compounds exhibit higher detonation values compared to TNT, which suggests that they ought to be prepared in a laboratory by skilled experimenters.

Methods

The stability of the C-NO2 link and the covalent character of the bonds have both been calculated using the atoms in molecule (AIM) method. The electronic structure calculations have been recovered at DFT method with aug-cc-pVDZ basis set using the Gaussian-16 quantum chemistry programme.

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

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

Data availability

All data generated or analysed during this study are included in this article.

References

  1. Mondal T et al (2009) On some strategies to design new high energy density molecules. J Mol Struct(THEOCHEM) 897:42

    CAS  Google Scholar 

  2. Agrawal JP (1998) Recent trends in high-energy materials. Prog Energy Combust Sci 24:1

    CAS  Google Scholar 

  3. Chavez D, Hill L, Hiskey M, Kinkead S (2000) Preparation and explosive properties of azo- and azoxy-furazans. J Energ Mater 18:219

    CAS  Google Scholar 

  4. Piao H et al (2015) Extensive theoretical studies on two new members of the FOX-7 family: 5-(dinitromethylene)-1{,}4-dinitramino-tetrazole and 1{,}1′-dinitro-4{,}4′-diamino-5{,}5′-bitetrazole as energetic compounds. Phys Chem Chem Phys 17:5840

    Google Scholar 

  5. Latypov NV et al (1998) Synthesis and reactions of 1,1-diamino-2,2-dinitroethylene. Tetrahedron 54:11525

    CAS  Google Scholar 

  6. Ostmark H et al (1998) FOX-7, A new explosive with low sensitivity and high performance. Naval Research, Department of the Navy, Washington, DC

    Google Scholar 

  7. Crawford MJ et al (2007) “ γ-FOX-7: structure of a high energy density material immediately prior to decomposition”, Propellants, Explosives. Pyrotechnics 32:478

    CAS  Google Scholar 

  8. Dorsett H (2000) Computational studies of FOX-7, a new insensitive explosive. DSTO-TR-1054, Australia

    Google Scholar 

  9. Ghanta S (2016) Theoretically predicted Fox-7 based new high energy density molecules. J Mol Struct 1118:28

    CAS  Google Scholar 

  10. Manna MS, Das CK, Ghanta S (2021) Design of C-H-N-O based new hetero-cyclic high energy density molecules: a theoretical survey. Struct Chem 32:1095

    CAS  Google Scholar 

  11. Ghanta S (2023) Design of derivatives of FOX-7-based new four-member heterocyclic insensitive high energy density molecules: a theoretical prospectives. J Mol Model 29:18

    CAS  Google Scholar 

  12. Sandstrom MM et al (2016) Small-scale thermal studies of volatile homemade explosives. Propellants Explos Pyrotech 41:14

    CAS  Google Scholar 

  13. Agrawal JP (2010) High energy materials: propellants, explosives, and pyrotechnics; Wiley- VCH Verlag GmbH & Co. KGaA: Weinheim, Germany

    Google Scholar 

  14. Chatterjee S et al (2017) Common explosives (TNT, RDX, HMX) and their fate in the environment: emphasizing bioremediation. Chemosphere 184:438

    CAS  PubMed  Google Scholar 

  15. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Petersson GA, Nakatsuji H, Li X, Caricato M, Marenich AV, Bloino J, Janesko BG, Gomperts R, Mennucci B, Hratchian HP, Ortiz JV et al (2016) Gaussian16 Revision C.01. Gaussian Inc. Wallingford CT

    Google Scholar 

  16. Tian L, Feiwu C (2012) Multiwfn: a multifunctional wavefunction analyzer. J Comput Chem 33:580

    Google Scholar 

  17. Badgujar DM, Talawar MB, Asthana SN, Mahulikar PP (2008) Advances in science and technology of modern energetic materials: an overview. J Hazard Mater 151:289–305

    CAS  PubMed  Google Scholar 

  18. Braithwaite PC, Edwards WW, Hajik RM, Highsmith TK, Lund GK, Wardle RB (1995) Proceedings of the International Symposium on Energetic Materials Technology. American Defense Preparedness Association Meeting 680:243–248

    Google Scholar 

  19. Lee KY, Chapman LB, Coburn MD (1987) 3-Nitro-l,2,4-triazoloneA: less sensitive explosive. J Energet Mater 5:27–33

    CAS  Google Scholar 

  20. Talwar M, Nair J, Palaiah R, Mukundan T, Singh H (2002) TEX: the new insensitive high explosive. Def Sci J 52(2):157–163. https://doi.org/10.14429/dsj.52.2160

    Article  CAS  Google Scholar 

  21. Pagoria PF, Mitchell AR, Schmidt RD, Simpson RL, Garcia F, Forbes J, Cutting J, Lee R, Swansiger R, Hoffman DM (1998) Presented at the Insensitive Munitions and Energetic Materials Technology Symposium, San Diego, CA

  22. Anniyappan M et al (2006) Synthesis, characterization and thermolysis of 1,1-diamino-2,2-dinitroethylene (FOX-7) and its salts. J Hazard Mater 137:812–819

    CAS  PubMed  Google Scholar 

  23. Lochert IJ (2003) Studies on FOX-7. NDIA Insensitive Munitions & Energetic Materials Technology Symposium, Orlando FL http://www.dtic.mil/ndia/2003insensitive/lochert2.pdf

    Google Scholar 

  24. Ramakrishnan VT, Vedachalam M, Boyer JH (1990) 4,10-Dinitro-2,7,8,12-tetraoxa-4,lOdiazatetracyclo [5.5.0.05.9, 03.]dodecane. Heterocycles 31:479–480

    CAS  Google Scholar 

  25. Koch E-C (2015) TEX – 4,10-Dinitro-2,6,8,12-tetraoxa-4,10-iazatetracyclo[5.5.0.05,9.03,11]-dodecane – review of a promising high density insensitive energetic material. Propellants Explos Pyrotech 40:374–387

    CAS  Google Scholar 

  26. Pagoria PF et al (1998) Synthesis, scale-up and characterization of 2,6-diamino-3,5-dinitropyrazine-l-oxide (LLM-105). JOWOG 9, Ald Ermaston, England June 22–26, 1998, April 27, 1998, http://www.osti.gov/bridge/servlets/purl/672328tIIGju/webviewablen/672328.pdf.

    Google Scholar 

  27. Pagoria PF et al (1998) Presented at the Insensitive Munitions and Energetic Materials Technology Symposium. San Diego, CA

    Google Scholar 

  28. Fried LE, Manaa MR, Pagoria PF, Simpson RL (2001) Design and synthesis of energetic materials. Annu Rev Mater Res 31:291–321

    CAS  Google Scholar 

  29. Schmidt RD et al (2001) Synthesis and properties of a new explosive, 4-amino-3,5-dinitro-1H-pyrazole, UCRL-ID-148510. Lawrence Livermore National Laboratory, USA, p 29

    Google Scholar 

  30. Schmidt RD et al (2001) Synthesis of 4-amino-3,5-dinitro-1H-pyrazole using vicarious nucleophilic substitution of hydrogen. J Heterocyclic Chem 38:1227–1230

    CAS  Google Scholar 

  31. Shevelev SA et al (1993) Nitropyrazoles. Russ Chem Bull 102:1063–1068

    Google Scholar 

  32. Pagoria PF et al (1998) Synthesis, scale-up and experimental testing of LLM-105 (2,6-diamino-3,5-dinitropyrazine-1-oxide). Insensitive Munitions and Energetic Materials Technology Symposium, San Diego, CA, USA

    Google Scholar 

  33. Klapötke TM, Witkowski TG (2016) Covalent and ionic insensitive high-explosives. Propellants, Explosives, Pyrotechnics 41:470–483

    Google Scholar 

  34. Koch E-C (2018) Nitroguanidine (NQ) – an underestimated insensitive energetic material for high explosives and propellants. 49th International Annual Conference of ICT, 26–29 June, Karlsruhe, Germany, V-3

    Google Scholar 

  35. Jousselin L (1877) Sur la nitrosoguanidine. Compt Rend 85:548–550

    Google Scholar 

  36. Pellizzari G (1891) Nitroguanidina. Gazz Chim 21:405–409

    Google Scholar 

  37. Thiele J (1892) Ueber Nitro- und Amidoguanidin. Ann Chem 270:1–63

    Google Scholar 

  38. Jackson CL, Wing JF (1888) LIX on tribromotrinitrobenzol. Am Chem J 10:283–287

    Google Scholar 

  39. Mitchell AR, Sanner RD (1993) Energetic materials—insensitivity and environmental awareness. In: Ebeling H (ed) Proceedings of the 24th International Annual Conference of ICT. Karlsruhe, Germany, p 38

    Google Scholar 

  40. Mitchell AR, Pagoria PF, Schmidt RD (1996) Energetic materials—technology, manufacturing and processing. In: Keicher T (ed) Proceedings of the 27th International Annual Conference of ICT. Karlsruhe, Germany, p 29

    Google Scholar 

  41. Mitchell AR, Pagoria PF, Schmidt RD (1997) Challenges in propulsion and combustion. In: Kuo KK (ed) 100 Years After Nobel. Bagell, New York, p 189

    Google Scholar 

  42. Östmark H et al (2002) N-guanylurea-dinitramide: a new energetic material with low sensitivity for propellants and explosives applications. Thermochim Acta 384:253–259

    Google Scholar 

  43. Sikder AK et al (2001) Studies on characterisation and thermal behaviour of 3-amino-5-nitro-1,2,4-triazole and its derivatives. J Hazard Mater 82:1–12

    CAS  PubMed  Google Scholar 

  44. Koch E-C (2016) Insensitive high explosives II: 3,3′-diamino-4,4′-azoxyfurazan (DAAF). Propellants Explos Pyrotech 41:526–538

    CAS  Google Scholar 

  45. Kamlet MJ, Jacobs SJ (1968) Chemistry of detonations. I. A simple method for calculating detonation properties of C-H-N-O explosives. J Chem Phys 48:23

    CAS  Google Scholar 

  46. Prince Jr ER (1976) Enthalpies of formation and calculated detonation properties of some thermally stable explosives. J Chem Eng Data 2(1):16–20

    Google Scholar 

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

    CAS  Google Scholar 

  48. Chengteh L, Weitao Y, Robert GP (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B 37:785

    Google Scholar 

  49. Ghanta S (2019) Pyrene radical cation and the diffuse interstellar band at 4430 Å: a theoretical survey. J Mol Struct 1191:32

    CAS  Google Scholar 

  50. Ghanta S (2016) Photophysics and photostability of pyrimidine molecule and its radical cation: a theoretical study. Mol Phys 114:2958–2973

    CAS  Google Scholar 

  51. Foster JP, Weinhold F (1980) Natural hybrid orbitals. J Am Chem Soc 102:7211

    CAS  Google Scholar 

  52. Chatterjee T, Sarma M, Ghanta S, Das SK (2011) Sterically driven electronic properties of naphthalene- and anthracene-end-capped 2,2′-bipyridine luminophores: synthesis and density functional theory. Tetrahedron Lett 52:5460

    CAS  Google Scholar 

  53. Roy TK et al (2007) Conformational preferences of mono-substituted cyclohydronitrogens: a theoretical study. J Mol Struct(THEOCHEM) 822:145

    CAS  Google Scholar 

  54. Rahman Z, Mahato M, Tohora N et al (2023) Spectroscopic and density functional studies on the interaction of a naphthalene derivative with anions. J Fluoresc 33:1027–1039

    CAS  PubMed  Google Scholar 

  55. Das N, Debnath P, Nandi NB et al (2023) Combined experimental and computational investigation of a Schiff base derived from N-(1-naphthyl) ethylenediamine for fluoride recognition. Monatsh Chem 154:1101–1114

    CAS  Google Scholar 

  56. Materials Studio, 2008, Accelrys Software Inc., San Diego, 2008.

    Google Scholar 

  57. Kamlet MJ, Ablard JE (1968) Chemistry of detonations. II. Buffered equilibria. J Chem Phys 48:36

    CAS  Google Scholar 

  58. Kamlet MJ, Dickinson C (1968) Chemistry of detonations. III. Evaluation of the simplified calculational method for Chapman-Jouguet detonation pressures on the basis of available experimental information. J Chem Phys 48:43

    CAS  Google Scholar 

  59. Kamlet MJ, Hurwitz H (1968) Chemistry of detonations. IV. Evaluation of a simple predictional method for detonation velocities of C–H–N–O explosives. J Chem Phys 48:3685

    CAS  Google Scholar 

  60. Chaoyang Z, Yuanjie S, Xiaodong Z, Haishan D, Xinfeng W (2005) Computational investigation on HEDM of azoic and azoxy derivatives of DAF, FOX-7, TATB, ANPZ and LLM-105. Theochem J Mol Struct 728:129

    Google Scholar 

  61. Chenzhong C, Shuo G (2007) Two dominant factors influencing the impact sensitivities of nitrobenzenes and saturated nitro compounds. J Phys Chem B 111:12399

    Google Scholar 

  62. Zhang XH, Yun ZH (1989) Explosive chemistry. National Defence Industry Press, Beijing

    Google Scholar 

  63. Dauber-Osguthorpe P, Roberts VA, Osguthorpe DJ, Wolff J, Genest M, Hagler AT (1988) Proteins: Struct., Funct. Bioinf 4:31

    CAS  Google Scholar 

  64. Gindulytė A, Massa L, Huang L, Karle J (1999) Proposed mechanism of 1,1-diamino-dinitroethylene decomposition: a density functional theory study. J Phys Chem A 103:11045

    Google Scholar 

  65. Kiselev VG, Gritsan NP (2014) Unexpected primary reactions for thermolysis of 1,1-diamino-2,2-dinitroethylene (FOX-7) revealed by ab initio calculations. J Phys Chem A 118:8002

    CAS  PubMed  Google Scholar 

  66. Proc (1998) Proceedings of the 11th international detonation symposium (ONR 2000), vol 807.

    Google Scholar 

  67. McKee ML (1986) Ab initio study of rearrangements on the nitromethane potential energy surface. J Am Chem Soc 108:5784

    CAS  PubMed  Google Scholar 

  68. Dewar MJS, Ritchie JP, Alster J (1985) Ground states of molecules. 65. Thermolysis of molecules containing NO2 groups. J Org Chem 50:1031

    CAS  Google Scholar 

  69. Wodtke AM, Hintsa EJ, Lee YT (1986) Infrared multiphoton dissociation of three nitroalkanes. J Phys Chem 90:3549

    CAS  Google Scholar 

  70. Kiselev VG, Gritsan NP (2008) Theoretical study of the nitroalkane thermolysis. 1. Computation of the formation enthalpy of the nitroalkanes, their isomers and radical products. J Phys Chem A 112:4458

    CAS  PubMed  Google Scholar 

  71. Keshavarz MH, Pouretedal HR (2004) Predicting detonation velocity of ideal and less ideal explosives via specific impulse, Indian. J Eng Mater Sci 11:429–432

    CAS  Google Scholar 

  72. Keshavarz MH et al (2009) A new computer code to evaluate detonation performance of high explosives and their thermochemical properties, part I. J Hazard Mater 172:1218–1228

    CAS  PubMed  Google Scholar 

Download references

Acknowledgements

SG is very much thankful to the National Institute of Technology Agartala and University of Hyderabad for computational facilities. This work is also supported by the NIT Agartala.

Author information

Authors and Affiliations

  1. Department of Chemical Engineering, National Institute of Technology Rourkela, Rourkela, Odisha, 769008, India

    Chandan Kumar Das

  2. Department of Chemical Engineering, National Institute of Technology, Agartala, Agartala, Tripura, 799046, India

    Mriganka Sekhar Manna

  3. Department of Chemistry, National Institute of Technology, Agartala, Agartala, Tripura, 799046, India

    Manas Roy, Nishan Das, Nishithendu Bikash Nandi & Susanta Ghanta

Authors
  1. Chandan Kumar Das
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mriganka Sekhar Manna
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Manas Roy
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Nishan Das
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Nishithendu Bikash Nandi
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Susanta Ghanta
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

C.K.Das: perform the work and analyse the work; M.S.Manna: perform the work and analsze the work; M. Roy: formal analysis and writing the manuscript; N. Das: perform the work; N.B. Nandi: formal analysis; S.Ghanta: design the work, checking the results, investigation, writing—review and editing.

Corresponding author

Correspondence to Susanta Ghanta.

Ethics declarations

Ethical approval

We wrote this research paper on our own. This academic paper has not been submitted anywhere. The contributions have the author’s consent.

Consent to participate

The authors consent to participate.

Consent to publish

The authors approved for publication. The published version has the author’s blessing. In order to guarantee that any concerns about the truthfulness or integrity of any portion of the work are duly examined and addressed, the authors agree to be responsible for all parts of the work.

Conflict of interest

The authors declare no competing interests.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Das, C.K., Manna, M.S., Roy, M. et al. Design of insensitive high explosives based on FOX-7: a theoretical prospectives. J Mol Model 29, 355 (2023). https://doi.org/10.1007/s00894-023-05769-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00894-023-05769-0

Keywords

Search

Navigation