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Reaction Mechanism and Energetics of Decomposition of Tetrakis(1,3-dimethyltetrazol-5-imidoperchloratomanganese(II)) from Quantum-Mechanics-based Reactive Dynamics

Cite this: J. Am. Chem. Soc. 2021, 143, 41, 16960–16975
Publication Date (Web):October 8, 2021
https://doi.org/10.1021/jacs.1c04847
Copyright © 2021 American Chemical Society

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    Abstract

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    Energetic materials (EMs) are central to construction, space exploration, and defense, but over the past 100 years, their capabilities have improved only minimally as they approach the CHNO energetic ceiling, the maximum energy density possible for EMs based on molecular carbon–hydrogen–nitrogen–oxygen compounds. To breach this ceiling, we experimentally explored redox-frustrated hybrid energetic materials (RFH EMs) in which metal atoms covalently connect a strongly reducing fuel ligand (e.g., tetrazole) to a strong oxidizer (e.g., ClO4). In this Article, we examine the reaction mechanisms involved in the thermal decomposition of an RFH EM, [Mn(Me2TzN)(ClO4]4 (3, Tz = tetrazole). We use quantum-mechanical molecular reaction dynamics simulations to uncover the atomistic reaction mechanisms underlying this decomposition. We discover a novel initiation mechanism involving oxygen atom transfer from perchlorate to manganese, generating energy that promotes the fission of tetrazole into chemically stable species such as diazomethane, diazenes, triazenes, and methyl azides, which further undergo exothermic decomposition to finally form stable N2, H2O, CO, CO2, Mn-based clusters, and additional incompletely combusted products.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.1c04847.

    • Additional computational details. Further discussion of initial time steps before and after heating to 2000 K. Additional discussion of pyrolysis at T = 3000 K. Additional snapshot images of pyrolysis structures and spin density plots, plots of spin densities in selected configurations, comparisons of energy and spin populations for PBE versus B3LYP, gas-phase geometries and energies (PDF)

    • Supporting Movie. Molecular dynamics of 3000 K pyrolysis (MP4)

    • Atomic coordinates from simulation files (ZIP)

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    Cited By

    This article is cited by 3 publications.

    1. James E. Allen, Sergey V. Zybin, Sergey I. Morozov, Owen T. O’Sullivan, Colton Kawamura, David E. Waxler, Joseph P. Hooper, William A. Goddard III, Michael J. Zdilla. High-Energy-Density Material with Magnetically Modulated Ignition. Journal of the American Chemical Society 2024, 146 (7) , 4500-4507. https://doi.org/10.1021/jacs.3c10621
    2. Chenze Chai, Qinghai Shu, Qiang Su, Jian Wang, Xijuan Lv, Dongxu Wang, Lixiang Zhong. Theoretical investigation on intermolecular interactions, co-crystal structure, thermal decomposition mechanism, and shock properties of 3-nitro-1,2,4-triazol-5-one (NTO) and ammonium perchlorate. CrystEngComm 2023, 25 (4) , 671-682. https://doi.org/10.1039/D2CE01554D
    3. Natalya Dolganina, Elena Ivanova, Roman Bilenko, Alexander Rekachinsky. HPC Resources of South Ural State University. 2022, 43-55. https://doi.org/10.1007/978-3-031-11623-0_4

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