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, William A. Goddard

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160 Citations (SciVal)


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
Issue number31
StatePublished - Aug 10 2005

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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