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Density functional calculations for a high energy density compound of formula C6H6−n (NO2) n

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Abstract

A series of polynitroprismanes, C6H6−n (NO2) n (n = 1–6) intended for use as high energy density compounds (HEDCs) were designed computationally. Their electronic structures, heats of formation, interactions between nitro groups, specific enthalpies of combustion, bond dissociation energies, and explosive performances (detonation velocities and detonation pressures) were calculated using density functional theory (DFT) with the 6-311 G** basis set. The results showed that all of the polynitroprismanes had high positive heats of formation that increased with the number of substitutions for the prismane derivatives, while the specific enthalpy of combustion decreased as the number of nitro groups increased. In addition, the range of enthalpy of combustion reducing is getting smaller. Interactions between ortho (vicinal) groups deviate from the group additivity rule and decrease as the number of nitro groups increases. In terms of thermodynamic stability, all of the polynitroprismanes had higher bond dissociation energies (BDEs) than RDX and HMX. Detonation velocities and detonation pressures were estimated using modified Kamlet–Jacobs equations based on the heat of detonation (Q) and the theoretical density of the molecule (ρ). It was found that ρ, D, and P are strongly linearly related to the number of nitro groups. Taking both their energetic properties and thermal stabilities into account, pentanitroprismane and hexanitroprismane are potential candidate HEDCs.

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Acknowledgments

This work is supported by the Natural Science Foundation of Shanxi Province (no. 2010021009-2), the Natural Science Foundation of China (no. 20871077), a research project supported by the Shanxi Scholarship Council of China (no. 201063), and the Natural Science Foundation of Shanxi Normal University.

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  1. School of Chemistry and Material Science, Shanxi Normal University, 041004, Linfen, China

    Wei-Jie Chi, Lu-Lin Li, Bu-Tong Li & Hai-Shun Wu

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  1. Wei-Jie Chi
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Correspondence to Bu-Tong Li.

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Chi, WJ., Li, LL., Li, BT. et al. Density functional calculations for a high energy density compound of formula C6H6−n (NO2) n . J Mol Model 18, 3695–3704 (2012). https://doi.org/10.1007/s00894-012-1367-6

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  • DOI: https://doi.org/10.1007/s00894-012-1367-6

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