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Atomistic-Scale Simulations of the Initial Chemical Events in the Thermal Initiation of Triacetonetriperoxide

van Duin, Adri C. T. and Zeiri, Yehuda and Dubnikova, Faina and Kosloff, Ronnie and Goddard, William A., III (2005) Atomistic-Scale Simulations of the Initial Chemical Events in the Thermal Initiation of Triacetonetriperoxide. Journal of the American Chemical Society, 127 (31). pp. 11053-11062. ISSN 0002-7863. doi:10.1021/ja052067y.

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To study the initial chemical events related to the detonation of triacetonetriperoxide (TATP), we have performed a series of molecular dynamics (MD) simulations. In these simulations we used the ReaxFF reactive force field, which we have extended to reproduce the quantum mechanics (QM)-derived relative energies of the reactants, products, intermediates, and transition states related to the TATP unimolecular decomposition. We find excellent agreement between the QM-predicted reaction products and those observed from 100 independent ReaxFF unimolecular MD cookoff simulations. Furthermore, the primary reaction products and average initiation temperature observed in these 100 independent unimolecular cookoff simulations match closely with those observed from a TATP condensed-phase cookoff simulation, indicating that unimolecular decomposition dominates the thermal initiation of the TATP condensed phase. Our simulations demonstrate that thermal initiation of condensed-phase TATP is entropy-driven (rather than enthalpy-driven), since the initial reaction (which mainly leads to the formation of acetone, O_2, and several unstable C_3H_6O_2 isomers) is almost energy-neutral. The O_2 generated in the initiation steps is subsequently utilized in exothermic secondary reactions, leading finally to formation of water and a wide range of small hydrocarbons, acids, aldehydes, ketones, ethers, and alcohols.

Item Type:Article
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van Duin, Adri C. T.0000-0002-3478-4945
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2005 American Chemical Society. Received 31 March 2005. Published online 19 July 2005. Published in print 1 August 2005. This research was supported by funding from ONR and DARPA-PROM (N00014-00-1-0839). The MSC computational facilities were provided by grants from ARO-DURIP and ONR-DURIP. Partial support for this research was obtained from funding by NATO (SFP 980873). We thank the reviewers for their constructive review of this manuscript.
Funding AgencyGrant Number
Office of Naval Research (ONR)N00014-00-1-0839
Defense Advanced Research Projects Agency (DARPA)UNSPECIFIED
Army Research Office (ARO)UNSPECIFIED
North Atlantic Treaty Organization (NATO)SFP 980873
Issue or Number:31
Record Number:CaltechAUTHORS:20170512-133829985
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Official Citation:Atomistic-Scale Simulations of the Initial Chemical Events in the Thermal Initiation of Triacetonetriperoxide Adri C. T. van Duin, Yehuda Zeiri, Faina Dubnikova, Ronnie Kosloff, and William A. Goddard, III Journal of the American Chemical Society 2005 127 (31), 11053-11062 DOI: 10.1021/ja052067y
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77422
Deposited By: Ruth Sustaita
Deposited On:12 May 2017 22:43
Last Modified:15 Nov 2021 17:30

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