Quantum-chemical Study of Some High-energy Azolo-bis(tetrazolo)azines
DOI:
https://doi.org/10.14529/cmse260204Keywords:
quantum chemical calculations, high-energy density materials, enthalpy of formation, tetracyclic compounds, tris(azolo)azines, tris(tetrazolo)[1,3,5]triazinesAbstract
High-energy compounds are widely used in various branches of industry and technology, which makes the development of new substances of this type and the study of their properties a relevant task. This work presents a quantum-chemical investigation of six high-energy tetracyclic compounds based on bis(tetrazolo)azines annelated with unsubstituted azoles. The aim of the study is to determine their key energetic characteristic, the gas-phase enthalpy of formation, and to analyze its dependence on molecular structure. Calculations were performed with Gaussian 09 using the B3LYP/6-311+G(2d,p) and B3LYP/cc-pVTZ density functional theory methods and the composite G4MP2 method, as well as with a G4MP2 implementation in the NWChem software package. Enthalpies of formation were determined using atomization and isodesmic reactions. The enthalpy of formation generally increases with the nitrogen content and the number of endothermic bonds in the annelated azole fragment; the highest value was obtained for tris(tetrazolo)-s-triazine. The NWChem G4MP2 implementation gives results in good agreement with Gaussian 09 calculations, while the use of several compute nodes reduces task execution time. Infrared spectra of the studied compounds were calculated and analyzed, and characteristic absorption bands were assigned to molecular structural fragments. Quantum-chemical calculations were performed using the "Lomonosov-2" supercomputer.
References
Rice B.M., Pai S.V., Hare J. Predicting heats of formation of energetic materials using quantum mechanical calculations. Combust. Flame. 1999. Vol. 118. P. 445–458. DOI: 10.1016/S0010-2180(99)00008-5.
Byrd E.F., Rice B.M. Improved prediction of heats of formation of energetic materials using quantum mechanical calculations. J. Phys. Chem. A. 2006. Vol. 110. P. 1005–1013. DOI: 10.1021/jp0536192.
Muthurajan H., Sivabalan R., Talawar M.B., et al. Prediction of heat of formation and related parameters of high energy materials. J. Hazard. Mater. 2006. Vol. 133. P. 30–45. DOI: 10.1016/j.jhazmat.2005.10.009.
Zhong L., Liu D., Hu M., et al. First-principles calculations of solid-phase enthalpy of formation of energetic materials. Commun. Chem. 2025. Vol. 8. P. 1–7. DOI: 10.1038/s42004-025-01544-9.
Larin A.A., Muravyev N.V., Pivkina A.N., et al. Assembly of tetrazolylfuroxan organic salts: Multipurpose green energetic materials with high enthalpies of formation and excellent detonation performance. Chem. Eur. J. 2019. Vol. 25. P. 4225–4233. DOI: 10.1002/chem.201806378.
Luk’yanov O.A., Parakhin V.V., Shlykova N.I., et al. Energetic N-azidomethyl derivatives of polynitro hexaazaisowurtzitanes series: CL-20 analogues having the highest enthalpy. New J. Chem. 2020. Vol. 44. P. 8357–8365. DOI: 10.1039/D0NJ01453B.
Gao H., Zhang Q., Shreeve J.M. Fused heterocycle-based energetic materials (2012–2019). J. Mater. Chem. A. 2020. Vol. 8. P. 4193–4216. DOI: 10.1039/c9ta12704f.
Wu J.T., Xu J., Li W., Li H.B. Coplanar fused heterocycle-based energetic materials. Propellants Explos. Pyrotech. 2020. Vol. 45, no. 4. P. 536–545. DOI: 10.1002/prep.201900333.
Wang S., Huang Y., Ma Q., Chen F.X. Theoretical research on tricyclic-based as high-energy performance energetic materials. J. Mol. Model. 2025. Vol. 31. P. 183. DOI: 10.1007/s00894-025-06401-z.
Kuznetsova A.N., Leonov N.E., Anikin O.V., et al. Parent 1,4-dihydro-[1,2,3]triazolo[4,5-d][1,2,3]triazole and its derivatives as precursors for the design of promising high energy density materials. New J. Chem. 2025. Vol. 49. P. 311–320. DOI: 10.1039/D4NJ04427D.
Volokhov V., Amosova E., Parakhin V., et al. Quantum-Chemical Study of Some Tris(pyrrolo)benzenes and Tris(pyrrolo)-1,3,5-triazines. Supercomputing. RuSCDays 2023. Vol. 14388 / ed. by V. Voevodin, S. Sobolev, M. Yakobovskiy, R. Shagaliev. Cham: Springer, 2023. P. 177–189. Lecture Notes in Computer Science. DOI: 10.1007/978-3-031-49432-1_14.
Volokhov V.M., Parakhin V.V., Amosova E.S., et al. Quantum-Chemical Study of Some Trispyrazolobenzenes and Trispyrazolo-1,3,5-triazines. Supercomput. Front. Innov. 2024. Vol. 11, no. 3. P. 64–73. DOI: 10.14529/jsfi240304.
Volokhov V., Amosova E., Parakhin V., et al. Quantum-Chemical Simulation of Some Triimidazolobenzenes and Triimidazolo-1,3,5-Triazines. Parallel Computational Technologies. PCT 2024. Vol. 2241 / ed. by L. Sokolinsky, M. Zymbler, V. Voevodin, J. Dongarra. Cham: Springer, 2024. P. 292–303. Communications in Computer and Information Science. DOI: 10.1007/978-3-031-73372-7_21.
Volokhov V.M., Parakhin V.V., Amosova E.S., et al. Comparison of Quantum-Chemical Programs and Methods for the Calculation of Enthalpies of Formation of High-Energy Tetracyclic Compounds. Supercomput. Front. Innov. 2025. Vol. 12, no. 2. P. 60–73. DOI: 10.14529/jsfi250205.
Volokhov V., Amosova E., Parakhin V., et al. Quantum-chemical study of unsubstituted tris(triazolo)benzenes and 1,3,5-triazines. Parallel Computational Technologies. PCT 2025. Vol. 2891 / ed. by L. Sokolinsky, M. Zymbler, V. Voevodin, J. Dongarra. Cham: Springer, 2026. P. 386–397. Communications in Computer and Information Science. DOI: 10.1007/978-3-032-22051-6_21.
Volokhov V.M., Parakhin V.V., Amosova E.S., et al. Quantum-chemical study of high energy derivatives of tris(triazolo)benzenes. Lobachevskii Journal of Mathematics. 2025. Vol. 46, no. 8. P. 3883–3894. DOI: 10.1134/S1995080225610100.
Volokhov V.M., Parakhin V.V., Amosova E.S., et al. Quantum-chemical study of high energy derivatives of tris(1,2,4-triazolo)-1,3,5-triazines. Lecture Notes in Computer Science. Vol. 16196. Cham: Springer, 2026. P. 159–171. DOI: 10.1007/978-3-032-13127-0_12.
Chen B., Lu H., Chen J., et al. revealing recent progress on nitrogen-rich energetic materials based on tetrazole skeleton. Top. Curr. Chem. 2023. Vol. 381. A. 25. DOI: 10.1007/s41061-023-00435-8.
Manzoor S., Yin X., Zhang J.G. Nitro-tetrazole based high performing explosives: Recent overview of synthesis and energetic properties. Defence Technology. 2021. Vol. 17. P. 1995–2010. DOI: 10.1016/j.dt.2021.02.002.
Volokhov V., Parakhin V., Amosova E., et al. Quantum-chemical calculations of the enthalpy of formation of isomeric 5/6/5 tricyclic tetrazolotetrazine derivatives annelated with nitroazoles. Supercomputing. RuSCDays 2024. Vol. 15406 / ed. by V. Voevodin, A. Antonov, D. Nikitenko. Cham: Springer, 2024. P. 187–201. Lecture Notes in Computer Science. DOI: 10.1007/978-3-031-78459-0_14.
Hammerl A., Klap¨otke T.M., Rocha R. Azide–tetrazole ring–chain isomerism in polyazido-1,3,5-triazines, triazido-s-heptazine, and diazidotetrazines. Eur. J. Inorg. Chem. 2006. P. 2210–2228. DOI: 10.1002/ejic.200600100.
Hu A., Zhang F. Ab initio molecular dynamics simulations on sensitivity of nitrogen-rich poly-tetrazolo energetic compounds. AIP Conference Proceedings. Vol. 1195, no. 1. American Institute of Physics, 2009. P. 809–812. DOI: 10.1063/1.3295265.
Hu A., Zhang F. A nitrogen-rich C3N12 solid transformed from cyanuric triazide under high pressure and temperature. J. Phys.: Condens. Matter. 2010. Vol. 22. A. 505402. DOI: 10.1088/0953-8984/22/50/505402.
Liang X.Q., Zhou J.J., Zheng Y., Ma F. Theoretical studies on the mechanism of the azido–tetrazole of azido-s-triazine. Natur. Prod. Commun. 2015. Vol. 10. P. 269–272. DOI: 10.1177/1934578x1501000213.
Frisch M.J., Trucks G.W., Schlegel H.B., et al. Gaussian 09, Revision B.01. Gaussian, Inc., Wallingford CT, 2010.
Valiev M., Bylaska E.J., Govind N., et al. NWChem: a comprehensive and scalable open-source solution for large scale molecular simulations. Comput. Phys. Commun. 2010. Vol. 181. P. 1477. DOI: 10.1016/j.cpc.2010.04.018.
Becke A.D. Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 1993. Vol. 98, no. 7. P. 5648–5652. DOI: 10.1063/1.464913.
Johnson B.J., Gill P.M.W., Pople J.A. The performance of a family of density functional methods. J. Chem. Phys. 1993. Vol. 98, no. 7. P. 5612–5626. DOI: 10.1063/1.464906.
Dunning T.H., Jr. Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen. J. Chem. Phys. 1989. Vol. 90, no. 2. P. 1007–1023. DOI: 10.1063/1.456153.
Curtiss L.A., Redfern P.C., Raghavachari K. Gaussian-4 theory using reduced order perturbation theory. J. Chem. Phys. 2007. Vol. 127, no. 12. A. 124105. DOI: 10.1063/1.2770701.
Curtiss L.A., Redfern P.C., Raghavachari K. Gn theory. Comput. Mol. Sci. 2011. Vol. 1, no. 5. P. 810–825. DOI: 10.1002/wcms.59.
Curtiss L.A., Redfern P.C., Raghavachari K. Gaussian-4 theory. J. Chem. Phys. 2007. Vol. 126, no. 8. P. 084108. DOI: 10.1063/1.2436888.
CCCBDB Vibrational Frequency Scaling Factors. URL: https://cccbdb.nist.gov/vsfx.asp (accessed: 25.12.2025).
NIST-JANAF Thermochemical Tables. URL: https://janaf.nist.gov/ (accessed: 25.12.2025).
Voevodin V.V., Antonov A.S., Nikitenko D.A., et al. Supercomputer Lomonosov-2: Largescale, deep monitoring and online analytics for the user community. Supercomput. Front. Innov. 2019. Vol. 6, no. 2. P. 4–11. DOI: 10.14529/jsfi190201.
Nikitenko D.A., Voevodin V.V., Zhumatiy S.A. Deep analysis of job state statistics on Lomonosov-2 supercomputer. Supercomput. Front. Innov. 2019. Vol. 5, no. 2. P. 4–10. DOI: 10.14529/jsfi180201.
