Self-accelerated mechanochemistry in nitroarenes

Maija M. Kuklja, Sergey N. Rashkeev

Research output: Contribution to journalArticle

28 Citations (Scopus)


The initiation of explosive decomposition in two energetic crystals, diamino-dinitroethylene (DADNE, C2H4N4O4) and triamino-trinitrobenzene (TATB, C6H6N6O6), was investigated using density functional theory. The initial chemical reactions in ideal TATB crystals were found to be determined by three main decomposition mechanisms that are almost unaffected by a shear-strain-induced deformation, C-NO2 homolysis, nitro-nitrite isomerization, and proton transfer. The two latter reactions are nearly isoenergetic and have lower activation energiesthan the first reaction. Atthe sametime, decomposition of DADNE is found to depend strongly on the molecular environment; molecules in ideal DADNE crystals favor nitro-nitrite isomerization, while molecules located at shear planes decompose via the C-NO2 homolysis pathway. We also established that the shear-strain accumulated in the DADNE dashboard-shaped molecular layers triggers an exothermic regime at fairl yearly stages of decomposition. In contrast, the structure of TATB that consists of flat, graphite-like molecular layers activates accelerated exothermal chemistry only at much higher concentrations of initial decomposition products.

Original languageEnglish
Pages (from-to)363-367
Number of pages5
JournalJournal of Physical Chemistry Letters
Issue number1
Publication statusPublished - 1 Jan 2010



  • Catalysis
  • Interfaces
  • Surfaces

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry

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