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Study on phonon spectra and heat capacities of CL-20/MTNP cocrystal and co-formers by density functional theory method

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Abstract

The phonon spectra and heat capacities of 2, 4, 6, 8, 10, 12-hexanitrohexaazaisowurtzitane/1-methyl-3, 4, 5-trinitropyrazole (CL-20/MTNP) cocrystal and co-formers were calculated in the framework of DFT. By analyzing the phonon density of states (DOS), the energy flow directions and trigger bonds of cocrystal and co-formers have been obtained and the microscopic physical nature was revealed for thermal decomposition mechanism, detonation performance, and sensitivity. For CL-20/MTNP cocrystal, the phonon number of “doorway” modes and the characteristic vibrational frequencies Δωd are between those of its co-formers, which can provide the microscopic understanding for the ordering of impact sensitivity at experiment, ε-CL-20 > CL-20/MTNP > MTNP. In CL-20/MTNP cocrystal, more phonons and stronger phonon DOS peaks of CL-20 molecules than those of MTNP molecules mean cocrystalʼs detonation performance is mainly dominated by CL-20 molecules. The heat capacities obtained by the Debye model rise with elevated temperatures at 0–600 K and the order is ε-CL-20 > CL-20/MTNP > MTNP.

The phonon spectra and heat capacities of CL-20/MTNP cocrystal and co-formers were calculated by density functional theory (DFT). In CL-20/MTNP cocrystal, the detonation performance and impact sensitivity are mainly dominated by CL-20 molecules. The broken bonds caused by energy transfer may undergo a multi-phonon pumping process.

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The data that support the findings of this study are available from the corresponding author upon reasonable request.

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Funding

This work was financially supported by Postgraduate Innovation Fund Project by Southwest University of Science and Technology (No.19ycx0026), National Natural Science Foundation of China (No.11572270), and Project of State Key Laboratory of Environmentally-Friendly Energy Materials, Southwest University of Science and Technology (No.18fksy0217).

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Authors and Affiliations

  1. State Key Laboratory of Environment-Friendly Energy Materials, Southwest University of Science and Technology, Mianyang, 621010, China

    Rong Guo, Xiao-Hui Duan & Chao Wu

  2. Xi’ an Modern Chemistry Research Institute, Xi’ an, 710065, China

    Jun Tao

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

    Hong-Zhen Li

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Guo, R., Tao, J., Duan, XH. et al. Study on phonon spectra and heat capacities of CL-20/MTNP cocrystal and co-formers by density functional theory method. J Mol Model 26, 148 (2020). https://doi.org/10.1007/s00894-020-04415-3

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