Reactivity of triacetone triperoxide and diacetone diperoxide: Insights from nuclear Fukui function

Abstract

Triacetone triperoxide (TATP) is more sensitive than diacetone diperoxide (DADP) in the solid-state explosion. To explain this reactivity difference, we analyzed the electronic structures and properties of the crystals of both compounds by using Ab initio method to calculate the structures of their individual molecules as well as their lattice structures and particularly calculating Nuclear Fukui function to gain insight into the sensitivity of the initial, rate-determining step of their decomposition. Our results indicate that TATP and DADP crystal structures exhibit significantly different electronic properties. Most notably, the electronic structure of the TATP crystal shows asymmetry among its reactive oxygen atoms as supported by magnitudes of their nuclear Fukui functions. The greater explosion sensitivity of crystalline TATP may be attributed to the properties of its electronic structure. The electronic calculations provided valuable insight into the decomposition sensitivity difference between TATP and DADP crystals.

Key words： nuclear Fukui function; electronic perturbation; Hellmann-Feynman force; organic crystals; unimolecular decomposition

Acknowledgment

This research was supported by NSF (DMR-0449633). PPZ thanks the financial support by the National Natural Science Foundation of China (Grant No. 21403097) and the Fundamental Research Funds for the Central Universities (lzujbky-2014-182). The authors would like to thank Dr. Shaoxin Feng for his technical supports on this project. TL also thanks Dr. Shubin Liu (UNC) for sharing his insights on DFT.

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