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

doi:10.1007/s11705-015-1507-5

Front. Chem. Sci. Eng.

2015, Vol. 9

Issue (1) : 114-123 https://doi.org/10.1007/s11705-015-1507-5

RESEARCH ARTICLE

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

Matthew J. SWADLEY¹,Panpan ZHOU²,Tonglei LI^3,^*(

)

1. Pharmaceutical Sciences, University of Kentucky, Lexington, Kentucky 40536, USA
2. Department of Chemistry, Lanzhou University, Lanzhou 730000, Gansu, China
3. Industrial & Physical Pharmacy, Purdue University, West Lafayette, Indiana 47907, USA

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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.

Keywords nuclear Fukui function electronic perturbation Hellmann-Feynman force organic crystals unimolecular decomposition

Corresponding Author(s): Tonglei LI

Issue Date: 07 April 2015

Cite this article:

Tonglei LI,Matthew J. SWADLEY,Panpan ZHOU. Reactivity of triacetone triperoxide and diacetone diperoxide: Insights from nuclear Fukui function[J]. Front. Chem. Sci. Eng., 2015, 9(1): 114-123.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-015-1507-5
https://academic.hep.com.cn/fcse/EN/Y2015/V9/I1/114

Fig.1 Molecular structures of (a) DADP and (b) TATP. Naming schemes correlate with data in Tables 1 and 2

Tab.1 Nuclear Fukui function magnitudes of atoms in TATP and DADP single molecules calculated in gas phase*

Tab.2 Nuclear Fukui function magnitudes of atoms in TATP and DADP crystals*

Fig.2 Vector representations of Φ α + (a, b) and Φ α - (c, d) of DADP single molecule (a, c) and TATP single molecule (b, d). Vector lengths (increasing in size with magnitude) and colors (blue to red in color with increasing magnitude) are scaled to the largest values of a molecule

Fig.3 Vector representations of Φ α + (a, b) and Φ α - (c, d) of DADP (a, c) and TATP (b, d) in their crystals. Vector lengths (increasing in size with magnitude) and colors (blue to red in color with increasing magnitude) are scaled to the largest values of a molecule

Fig.4 Molecular electrostatic potential (MEP) maps of (a) DADP and (b) TATP on the isosurface of electron density (0.001 a.u.). The values of the MEP (a.u.) are marked by the color bar

Fig.5 Highest occupied molecular orbitals (HOMOs) of (a) DADP and (c) TATP single molecules, and lowest unoccupied molecular orbitals (LUMOs) of (b) DADP and (d) TATP

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