Atomistic-scale simulations of the initial chemical events in the thermal initiation of triacetonetriperoxide

A. C T Van Duin, Yehuda Zeiri, Faina Dubnikova, Ronnie Kosloff, William A. Goddard

Research output: Contribution to journalArticle

141 Citations (Scopus)

Abstract

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, Oa, and several unstable C 3H6O2 isomers) is almost energy-neutral. The O2 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.

Original languageEnglish (US)
Pages (from-to)11053-11062
Number of pages10
JournalJournal of the American Chemical Society
Volume127
Issue number31
DOIs
StatePublished - Aug 10 2005

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Quantum theory
Reaction products
Molecular dynamics
Hot Temperature
Decomposition
Computer simulation
Detonation
Aldehydes
Ketones
Acetone
Isomers
Enthalpy
Ethers
Molecular Dynamics Simulation
Mechanics
Alcohols
Entropy
Hydrocarbons
Acids
Water

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Van Duin, A. C T ; Zeiri, Yehuda ; Dubnikova, Faina ; Kosloff, Ronnie ; Goddard, William A. / Atomistic-scale simulations of the initial chemical events in the thermal initiation of triacetonetriperoxide. In: Journal of the American Chemical Society. 2005 ; Vol. 127, No. 31. pp. 11053-11062.
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abstract = "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, Oa, and several unstable C 3H6O2 isomers) is almost energy-neutral. The O2 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.",
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Atomistic-scale simulations of the initial chemical events in the thermal initiation of triacetonetriperoxide. / Van Duin, A. C T; Zeiri, Yehuda; Dubnikova, Faina; Kosloff, Ronnie; Goddard, William A.

In: Journal of the American Chemical Society, Vol. 127, No. 31, 10.08.2005, p. 11053-11062.

Research output: Contribution to journalArticle

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AU - Van Duin, A. C T

AU - Zeiri, Yehuda

AU - Dubnikova, Faina

AU - Kosloff, Ronnie

AU - Goddard, William A.

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