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NTO degradation by direct photolysis: DFT study

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Abstract

NTO (5-nitro-1,2,4-triazol-3-one) represents high explosive material, which is increasingly being used in formulations of insensitive munitions such as IMX-101 and IMX-104. Environmental fate of energetic materials has gained particular interest since they could pollute ground water. After being released to the environment, NTO undergoes different biotic and abiotic transformation. Photolysis represents potentially significant degradation pathway for NTO in the environment, and understanding the reactions of its photo-transformation is vital. A detailed investigation of possible pathways for direct photolysis of NTO in aqueous solution was performed by computational study at PCM(Pauling)/M06-2X/6–311 +  + G(d,p) theory level. Decomposition of NTO is a multistep process that may begin with nitro-nitrite rearrangement and interaction with water resulting in nitro group substitution. The investigated pathways reveal urazole, semicarbazide, isocyanic acid, and diazene as intermediates of the considered processes. Results show significant increase in reactivity of NTO and its intermediates in triplet state, as compared to singlet-state reactions. Homolytic bond rupture reactions greatly contribute to the studied photodecomposition pathways.

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Data availability

The data supporting the findings of this study are available within its supplementary material and from the corresponding author on reasonable request.

Code availability

Gaussian 09 package program.

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Funding

This work was supported by the US Army Research Office (ARO) (grant number is W911NF-20–1-0116). The computation time was provided by the Extreme Science and Engineering Discovery Environment (XSEDE) (award allocation number DMR110088).

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Authors and Affiliations

  1. Interdisciplinary Center for Nanotoxicity, Department of Chemistry, Physics & Atmospheric Sciences, Jackson State University, Jackson, MS, 39217, USA

    Liudmyla K. Sviatenko & Jerzy Leszczynski

  2. Institute of Molecular Biology and Genetics, NAS of Ukraine, 150 Zabolotny Str, Kyiv, 03143, Ukraine

    Leonid Gorb

Authors
  1. Liudmyla K. Sviatenko
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  2. Leonid Gorb
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  3. Jerzy Leszczynski
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Contributions

LS calculated and interpreted data and was a contributor in writing the manuscript. LG interpreted data and was a contributor in writing the manuscript. JL interpreted data and was a contributor in writing and editing the manuscript. All authors read and approved the final manuscript.

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Correspondence to Liudmyla K. Sviatenko or Jerzy Leszczynski.

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Author JL is the Editor and receives no compensation as member of the board of directors. The other authors declare no competing interests.

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Sviatenko, L.K., Gorb, L. & Leszczynski, J. NTO degradation by direct photolysis: DFT study. Struct Chem 34, 23–31 (2023). https://doi.org/10.1007/s11224-022-01923-1

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