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Coupling of temperature with pressure induced initial decomposition mechanisms of two molecular crystals: An ab initio molecular dynamics study

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Abstract

Ab initio molecular dynamics simulations were performed to study the initiation of decomposition and formation of first products of two molecular crystals pentaerythritol tetranitrate (PETN) and 5-nitro-2,4-dihydro-1,2,4-triazole-3-one (NTO) under thermal decomposition temperature (475 K for PETN and 531 K for NTO) coupled with different pressures (1-5 GPa). The pressure effects on the initial decomposition steps and initially generated products on PETN and NTO were very different. PETN was triggered by C-H ⋯O intermolecular hydrogen transfer. The initial decomposition mechanism was independent of the pressure. For NTO, two different initial decomposition mechanisms were found. At 1, 2, and 3 GPa, it was triggered by N-H ⋯O intermolecular hydrogen transfer, while at 4 and 5 GPa, it was triggered by N-H ⋯N intermolecular hydrogen transfer. This indicates that the initial decomposition mechanism was dependent on the pressure. Our study may provide new insights into initial mechanisms and decomposition reactions of molecular crystal explosives under thermal decomposition temperature coupled with different pressures with details at atomic level.

PETN was triggered by C-H∙∙∙O intermolecular hydrogen transfer; NTO was triggered by N-H∙∙∙O intermolecular hydrogen transfer.

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Acknowledgments

This work was supported by the National Natural Science Foundation of China (Grant No. 21273115), the NSAF Foundation of National Natural Science Foundation of China and China Academy of Engineering Physics (Grant No. U12301020), and a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.

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Authors and Affiliations

  1. Institute for Computation in Molecular and Materials Science and Department of Chemistry, School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, China

    QIONG WU, DONG XIANG, GUOLIN XIONG, WEIHUA ZHU & HEMING XIAO

  2. School of Materials Science and Engineering, Nanjing Institute of Technology, Nanjing, 211167, China

    QIONG WU

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  1. QIONG WU
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  2. DONG XIANG
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  3. GUOLIN XIONG
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  4. WEIHUA ZHU
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Correspondence to WEIHUA ZHU.

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WU, Q., XIANG, D., XIONG, G. et al. Coupling of temperature with pressure induced initial decomposition mechanisms of two molecular crystals: An ab initio molecular dynamics study. J Chem Sci 128, 695–705 (2016). https://doi.org/10.1007/s12039-016-1068-2

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  • DOI: https://doi.org/10.1007/s12039-016-1068-2

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