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A DFT approach towards understanding the thermal stability of TKX-50 and their key precursors through band gaps and MESP

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Abstract

TKX-50 (dihydroxylammonium 5,5′-bistetrazolate-1,1′-dioxide) is a recent time invention by Klapotke et. al. in the field of high energy materials, and it outperforms all the existing materials by means of performance parameters. It is rising as potential energetic material due to favorable thermal insensitivity, low toxicity and safe handling. The decomposition temperature (Tmax) values of precursors such as glyoxime (I), 1,2-dichloroglyoxime (II), 1,2-diazidoglyoxime (III), and bistetrazoledihydroxide (IV) and ending products TKX-50 (V) and ABTOX (VI) have been attempted to correlate with the results obtained from molecular electrostatic potentials and band gaps calculated from the difference of ionization potential and electron affinity. The molecular electrostatic potential values of azido attached -NO group of III are much less than that of hydro/chloro attached -NO group of I/II and that of tetrazole groups IV, V, and VI. The band gaps calculated from stability trend in the increasing order of III < II < I < IV < V < VI are well corroborated with stability trend drawn from experimentally determined decomposition temperatures. Further, employing conceptual density functional theory (DFT) molecular descriptors, band gap values were calculated via the difference of ionization potential and electron affinity to understand the thermal stability of TKX-50, ABTOX, and its precursors.

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The online version of this article contains supplementary material, which is available to authorized users. It contains absolute electronic energies and Cartesian coordinates of all the optimized stationary points at wb97xd/6–311 +  + g(3df,3pd) in the gas phase including corresponding charge and multiplicity.

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Acknowledgements

The authors thank the director of HEMRL, Pune, for his constant encouragement to undertake work on TKX-50.

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Authors and Affiliations

  1. CEPP Division, High Energy Materials Research Laboratory, Sutarwadi, Pune, 411 021, India

    P. K. Adak, Sunil Kumar Singh, Jaivindra Singh, Siribattula Mahesh, M. K. Jain, P. Anand Kumar Sagar & Md Abdul Shafeeuulla Khan

  2. Defence Institute of Advanced Technology (Defence Research & Development Organization), Girinagar, Pune, 411 025, India

    P. K. Adak & Shaibal Banerjee

Authors
  1. P. K. Adak
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  2. Sunil Kumar Singh
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  3. Jaivindra Singh
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  4. Siribattula Mahesh
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  6. P. Anand Kumar Sagar
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  8. Md Abdul Shafeeuulla Khan
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Contributions

All authors contributed to the study conception, design data collection, and analysis. The first draft of the manuscript was written by Md Abdul Shafeeuulla Khan, and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to P. K. Adak or Md Abdul Shafeeuulla Khan.

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Adak, P.K., Singh, S.K., Singh, J. et al. A DFT approach towards understanding the thermal stability of TKX-50 and their key precursors through band gaps and MESP. J Mol Model 28, 400 (2022). https://doi.org/10.1007/s00894-022-05398-z

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