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Easy methods to study the smart energetic TNT/CL-20 co-crystal

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Abstract

2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) is a high-energy nitramine explosive with high mechanical sensitivity. 2,4,6-trinitrotoluene (TNT) is insensitive but by no means a high performance explosive. To reveal the significant importance and smart-material functionality of the energetic-energetic co-crystals, the stability, mechanical and explosive properties TNT/CL-20 co-crystal, TNT crystal and CL-20 crystal were studied. Non-hydrogen bonded non-covalent interactions govern the structures of energetic-energetic co-crystals. However, it is very difficult to accurately calculate the non-covalent intermolecular interaction energies. In this paper, the local conformation and the intricate non-covalent interactions were effectively mapped and analyzed from the electron density (ρ) and its derivatives. The results show that the two components TNT and CL-20 are connected mainly by nitro–aromatic interactions, and nitro–nitro interactions. The steric interactions in TNT/CL-20 could not be confronted with the attractive interactions. Moreover, the scatter graph of TNT crystal reveals the reason why TNT is brittle. The detailed electrostatic potential analysis predicted that the detonation velocities (D) and impact sensitivity for the compounds both increase in the sequence of CL-20 > TNT/CL-20 co-crystal > TNT. Additionally, TNT/CL-20 co-crystal has better malleability than its pure components. This demonstrates the capacity and the feasibility of realizing explosive smart materials by co-crystallization, even if strong hydrogen bonding schemes are generally lacking in energetic materials.

Scatter graph (left) and gradient isosurface (right) of intermolecular interactions in TNT/CL-20 co-crystal

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Acknowledgments

The authors are grateful for financial support from National Natural Science Foundation of China—CAEP project (No. 11076002).

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Authors and Affiliations

  1. Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang, 621900, China

    Huarong Li, Yuanjie Shu, Ling Chen & Qing Ma

  2. Department of Chemistry, Nanjing University of Science and Technology, Nanjing, 210094, China

    Huarong Li, Qing Ma & Xuehai Ju

  3. TCM Comprehensive Experiment Teaching Center, Shandong University of Chinese Medicine, Shandong, 250355, China

    Shijie Gao

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  1. Huarong Li
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Correspondence to Yuanjie Shu.

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Li, H., Shu, Y., Gao, S. et al. Easy methods to study the smart energetic TNT/CL-20 co-crystal. J Mol Model 19, 4909–4917 (2013). https://doi.org/10.1007/s00894-013-1988-4

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  • DOI: https://doi.org/10.1007/s00894-013-1988-4

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