Self-accelerated mechanochemistry in nitroarenes

Maija M. Kuklja, Sergey Rashkeev

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

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
Volume1
Issue number1
DOIs
Publication statusPublished - 1 Jan 2010
Externally publishedYes

Fingerprint

Nitrites
Trinitrobenzenes
Decomposition
Graphite
Shear strain
Protons
Isomerization
Crystals
Molecules
Proton transfer
Density functional theory
Chemical reactions
Chemical activation

Keywords

  • Catalysis
  • Interfaces
  • Surfaces

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Self-accelerated mechanochemistry in nitroarenes. / Kuklja, Maija M.; Rashkeev, Sergey.

In: Journal of Physical Chemistry Letters, Vol. 1, No. 1, 01.01.2010, p. 363-367.

Research output: Contribution to journalArticle

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