Reactivity of triacetone triperoxide and diacetone diperoxide: Insights from nuclear Fukui function
- 131 Downloads
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.
Keywordsnuclear Fukui function electronic perturbation Hellmann-Feynman force organic crystals unimolecular decomposition
Unable to display preview. Download preview PDF.
- 6.White G M. An explosive drug case. Journal of Forensic Sciences, 1992, 37(2): 652–656Google Scholar
- 8.Parr R G, Yang W. Density-functional theory of atoms and molecules. New York: Oxford University Press, 1989Google Scholar
- 14.Hellmann H. Einfuhrung in die quantencheie. Deuticke, Vienna, 1937Google Scholar
- 17.Pacheco-Londono L C, Primera-Pedrozo O M, Hernandez-Rivera S P. Experimental and theoretical model of reactivity and vibrational detectrion modes of triacetone triperoxide (TATP) and homologues. Proceedings of the SPIE-The International Society for Optical Engineering, 2004, 5617: 190–201Google Scholar
© Higher Education Press and Springer-Verlag Berlin Heidelberg 2015