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Correlation between molecular charge densities and sensitivity of nitrogen-rich heterocyclic nitroazole derivative explosives

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Abstract

Nitroazole derivatives are nitrogen-rich heterocyclic ring molecules with potential application as energetic materials. Thirty-three of them—nitroimidazoles, nitrotriazoles, and nitropyrazoles—were investigated. Computed density functional theory molecular charge densities were partitioned employing the accurate distributed multipole analysis (DMA) method. Based on the magnitude of the DMA atom-centered electric multipoles (monopole, dipole, and quadrupole values), mathematical models were developed to compute the impact sensitivity of the explosives composed of these molecules. Charge localization and delocalization of the ring nitrogen atoms as well as charges of the atoms of the nitro group affect the sensitivity of explosives composed of nitroazole derivatives. The sensitivity is strongly dependent on the ring position of the nitrogen atoms and the bonding site of the substituent groups. The N/C ratio and the repulsion of the non-bonding electron pairs of the vicinal nitrogen atoms of the ring also play an important role in the stability of nitroazoles. The influence of the withdrawing group (NO2) and the electron injector groups (NH2 and CH3) including their bonding position on the ring could be quantified.

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Funding

We thank the Brazilian National Research Council (CNPq) through research grants 304148/2018-0 and 409447/2018-8 and the Brazilian Army for the support of this work.

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  1. Departamento de Química, Instituto Militar de Engenharia, Praça General Tibúrcio, 80, Rio de Janeiro, RJ, 22290-270, Brazil

    Roberta Siqueira Soldaini de Oliveira & Itamar Borges Jr

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  1. Roberta Siqueira Soldaini de Oliveira
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de Oliveira, R.S.S., Borges, I. Correlation between molecular charge densities and sensitivity of nitrogen-rich heterocyclic nitroazole derivative explosives. J Mol Model 25, 314 (2019). https://doi.org/10.1007/s00894-019-4195-0

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