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Theoretical investigations on the density, detonation performance and stability of fluorinated hexanitroadamantanes

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Abstract

Cage compounds such as hexanitroadamantane (HNA) and hexanitrohexaazaisowurtzitane (HNIW, CL-20) constitute an important category of energetic compounds owing to the strained compact cage structure. Introduction of energetic substituents on the cage skeleton can further improve their energetic performance. In this paper, 24 substituted derivatives of fluorine-containing energetic groups of HNA are studied at the M06-2X/6-31G* level of density functional theory. The densities close to the experimental values are obtained by using the fitting equation. Based on the calculated densities and heats of formation, detonation properties are predicted using the modified Kamlet-Jacobs equations according to the largest exothermic principle. The contribution to detonation performance of various groups has the order of –C(NO2)2NF2 > –SF5 > –C(NO2)2F > –NF2 > –OCF3 > –CF3 > –F > –SCF3. As more fluorine-containing groups being introduced, detonation velocities and pressures increase quickly. Thermal stability has been discussed by the bond dissociation energies. The C-NO2 bond is the trigger bond of all the studied compounds. According to the energetics and stability criteria as a high energy density compound (HEDC), B2, B3, B7, C2, and C7 are the good candidates. The influences of the fluorine-containing groups found in this study will be beneficial to design of new fluorinated HEDCs by modifying structure.

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Funding

One of the coauthors (G. X. Wang) acknowledges research funding from the National Natural Science Foundation of China (No. 21403110).

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Authors and Affiliations

  1. Computation Institute for Molecules and Materials, Department of Chemistry, Nanjing University of Science and Technology, Nanjing, 210094, China

    Yimin Xu, Guixiang Wang, Yan Liu & Xuedong Gong

  2. National Quality Supervision and Inspection Center for Industrial Explosive Materials, Nanjing, 210094, China

    Pin Gao

Authors
  1. Yimin Xu
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  2. Guixiang Wang
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  3. Yan Liu
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  4. Pin Gao
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  5. Xuedong Gong
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Correspondence to Guixiang Wang or Xuedong Gong.

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The Multiwfn program can be obtained from “http://sobereva.com/multiwfn/”.

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Xu, Y., Wang, G., Liu, Y. et al. Theoretical investigations on the density, detonation performance and stability of fluorinated hexanitroadamantanes. Struct Chem 32, 1651–1657 (2021). https://doi.org/10.1007/s11224-021-01729-7

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  • DOI: https://doi.org/10.1007/s11224-021-01729-7

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