DFT studies on nitrogen-rich pyrazino [2, 3-e] [1, 2, 3, 4] tetrazine–based high–energy density compounds
By using the density functional theory method, we investigated the heats of formation (HOFs), electronic structure, detonation properties, thermal stability and sensitivity for a set of pyrazino [2, 3-e] [1, 2, 3, 4] tetrazine derivatives with different substituents and different numbers of N-oxides. Our findings reveal that the HOFs of the derivatives decrease dramatically with the increasing number of N-oxides. The effects of the substituents on the HOMO-LUMO gaps are coupled with those of the N-oxides. The calculated detonation properties point out that −NF2, −ONO2 and an increasing number of N-oxides are very helpful for improving the detonation performance of the designed derivatives. The bond dissociation energies of the weakest bonds indicate that a majority of our designed compounds have better thermal stability. The −NH2 group is very useful to decrease the free space value. Most of the derivatives have higher h50 values compared with parent molecules. Considering the sensitivity, thermal stability and detonation performance, four compounds could be considered as potential candidates of high–energy density compounds.
KeywordsDensity functional theory Pyrazino [2, 3-e] [1, 2, 3, 4] tetrazine derivatives N-Oxide Heats of formation Detonation properties Bond dissociation energy Impact sensitivity
This work was supported by the National Natural Science Foundation of China (Grant No. 21773119) and Science Challenging Program (No. TZ2016001).
- 1.Millar RW, Philbin SP, Claridge RP, Hamid J (2004) Studies of novel heterocyclic insensitive high explosive compounds: pyridines, pyrimidines, pyrazines and their bicyclic analogues. Propellants, Explosives, Pyrotechnics: An International Journal Dealing with Scientific and Technological Aspects of Energetic Materials 29(2):81–92CrossRefGoogle Scholar
- 3.Pichtel J (2012) Distribution and fate of military explosives and propellants in soil: a review. Applied and Environmental Soil Science:2012Google Scholar
- 5.He P, Zhang J-G, Wang K, Yin X, Jin X, Zhang T-L (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(8):5840–5848CrossRefGoogle Scholar
- 15.Pagoria PF, Lee GS, Mitchell AR, Schmidt R (2001) Synthesis of amino- and nitro-substituted heterocycles as insensitive energetic materials. Lawrence Livermore National Lab, CA (US)Google Scholar
- 50.Dechant J (1988) Quantities, units and symbols in physical chemistry. Compiled for the Commission on Physicochemical Symbols, Terminology, and Units, Physical Chemistry Division, International Union of Pure and Applied Chemistry, by I. MILLS, T. CVITAŠ, K. HOMANN, N. KALLAY and K. KUCHITSU. ISBN 0-632-01773-2. Oxford: Blackwell Scientific Publications 1988. IX, 134 pp., cloth,£ 19.95. Acta Polymerica 39(10):598–598Google Scholar
- 52.Frisch M, Trucks G, Schlegel H, Scuseria G, Robb M, Cheeseman J, Scalmani G, Barone V, Mennucci B, Petersson G (2009) Gaussian 09 package. Pittsburgh PA: Gaussian IncGoogle Scholar
- 54.Zhang X, Zhu W, Xiao H (2010) Theoretical studies on heats of formation, detonation properties, and bond dissociation energies of monofurazan derivatives. Int J Quantum Chem 110(8):1549–1558Google Scholar
- 57.Smith MW, Cliff MD (1999) NTO-based explosive formulations: a technology review. DEFENCE SCIENCE AND TECHNOLOGY ORGANISATION CANBERRA (AUSTRALIA),Google Scholar