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

Zybin, Sergey V. and Morozov, Sergey I. and Prakash, Prabhat and Zdilla, Michael J. and Goddard, William A., III (2021) Reaction Mechanism and Energetics of Decomposition of Tetrakis(1,3-dimethyltetrazol-5-imidoperchloratomanganese(II)) from Quantum-Mechanics-based Reactive Dynamics. Journal of the American Chemical Society, 143 (41). pp. 16960-16975. ISSN 0002-7863. doi:10.1021/jacs.1c04847. https://resolver.caltech.edu/CaltechAUTHORS:20211012-211827323

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Abstract

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.1c04847DOIArticle
ORCID:
AuthorORCID
Morozov, Sergey I.0000-0001-6226-5811
Prakash, Prabhat0000-0003-1430-2379
Zdilla, Michael J.0000-0003-0212-2557
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2021 American Chemical Society. Received: May 25, 2021; Published: October 8, 2021. The Caltech research was supported by a research grant from ONR (N00014-19-1-2081). The Temple research was supported by a research grant from ONR (N00014-19-1-2087). Temple University’s HPC resources were supported in part by the National Science Foundation through major research instrumentation grant number 1625061 and by the U.S. Army Research Laboratory under contract number W911NF-16-2-0189. S.M. is thankful for the support by the Supercomputer Simulation Laboratory of the South Ural State University.(51) Author Contributions: The manuscript was written through contributions of all authors. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Office of Naval Research (ONR)N00014-19-1-2081
Office of Naval Research (ONR)N00014-19-1-2087
NSFCNS-1625061
Army Research LaboratoryW911NF-16-2-0189
South Ural State UniversityUNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1494
Issue or Number:41
DOI:10.1021/jacs.1c04847
Record Number:CaltechAUTHORS:20211012-211827323
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20211012-211827323
Official Citation:Reaction Mechanism and Energetics of Decomposition of Tetrakis(1,3-dimethyltetrazol-5-imidoperchloratomanganese(II)) from Quantum-Mechanics-based Reactive Dynamics. Sergey V. Zybin, Sergey I. Morozov, Prabhat Prakash, Michael J. Zdilla, and William A. Goddard. Journal of the American Chemical Society 2021 143 (41), 16960-16975; DOI: 10.1021/jacs.1c04847
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:111372
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:14 Oct 2021 14:29
Last Modified:18 Nov 2021 22:55

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