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.

Graphical abstract

Keywords

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

References

[1] Dubnikova F, Kosloff R, Almog J, Zeiri Y, Boese R, Itzhaky H, Alt A, Keinan E. Decomposition of triacetone triperoxide is an entropic explosion. Journal of the American Chemical Society, 2005, 127(4): 1146–1159

[2] Oxley J C, Smith J L, Chen H. Decomposition of a multi-peroxidic compound: Triacetone triperoxide (tatp). Propellants, Explosives, Pyrotechnics, 2002, 27(4): 209–216

[3] Sanderson J R, Story P R. Macrocyclic synthesis. The thermal decomposition of dicyclohexylidene diperoxide and tricyclohexylidene triperoxide. Journal of Organic Chemistry, 1974, 39(24): 3463–3469

[4] van Duin A C T, Zeiri Y, Dubnikova F, Kosloff R, Goddard W A. Atomistic-scale simulations of the initial chemical events in the thermal initiation of triacetonetriperoxide. Journal of the American Chemical Society, 2005, 127(31): 11053–11062

[5] Evans H E, Tulleners F A J, Sanchez B L, Rasmussen C A. An unusual explosive, triacetone triperoxide. Journal of Forensic Sciences, 1986, 31(3): 1119–1125

[6] White G M. An explosive drug case. Journal of Forensic Sciences, 1992, 37(2): 652–656

[7] Politzer P, Murray J S. The fundamental nature and role of the electrostatic potential in atoms and molecules. Theoretical Chemistry Accounts, 2002, 108(3): 134–142

[8] Parr R G, Yang W. Density-functional theory of atoms and molecules. New York: Oxford University Press, 1989

[9] Parr R G, Yang W T. Density-functional theory of the electronic-structure of molecules. Annual Review of Physical Chemistry, 1995, 46(1): 701–728

[10] Kohn W, Becke A D, Parr R G. Density functional theory of electronic structure. Journal of Physical Chemistry, 1996, 100(31): 12974–12980

[11] Geerlings P, De Proft F, Langenaeker W. Conceptual density functional theory. Chemical Reviews, 2003, 103(5): 1793–1873

[12] DeProft F, Liu S B, Geerlings P. Calculation of the nuclear fukui function and new relations for nuclear softness and hardness kernels. Journal of Chemical Physics, 1998, 108(18): 7549–7554

[13] Feynman R P. Forces in Molecules. Physical Review, 1939, 56(4): 340–343

[14] Hellmann H. Einfuhrung in die quantencheie. Deuticke, Vienna, 1937

[15] Cohen M H, Gandugliapirovano M V, Kudrnovsky J. Electronic and nuclear-chemical reactivity. Journal of Chemical Physics, 1994, 101(10): 8988–8997

[16] Luty T, Ordon P, Eckhardt C J. A model for mechanochemical transformations: Applications to molecular hardness, instabilities, and shock initiation of reaction. Journal of Chemical Physics, 2002, 117(4): 1775–1785

[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: 190–201

[18] Ayers P W. The physical basis of the hard/soft acid/base principle. Faraday Discussions, 2007, 135: 161–190

[19] Ghanty T K, Ghosh S K. Correlation between hardness, polarizability, and size of atoms, molecules, and clusters. Journal of Physical Chemistry, 1993, 97(19): 4951–4953

[20] Feng S X, Li T L. Understanding solid-state reactions of organic crystals with density functional theory-based concepts. Journal of Physical Chemistry A, 2005, 109(32): 7258–7263

[21] Li T L, Feng S X. Study of crystal packing on the solid-state reactivity of indomethacin with density functional theory. Pharmaceutical Research, 2005, 22(11): 1964–1969

[22] Hohenberg P, Kohn W. Inhomogeneous electron gas. Physical Review B: Condensed Matter and Materials Physics, 1964, 136(3B): 864–871

[23] Guerra M. On the use of diffuse functions for estimating negative electron-affinities with lcao methods. Chemical Physics Letters, 1990, 167(4): 315–319

[24] Galbraith J M, Schaefer H F. Concerning the applicability of density functional methods to atomic and molecular negative ions. Journal of Chemical Physics, 1996, 105(2): 862–864

[25] De Proft F, Sablon N, Tozer D J, Geerlings P. Calculation of negative electron affinity and aqueous anion hardness using kohn-sham homo and lumo energies. Faraday Discussions, 2007, 135: 151–159

[26] Tozer D J, De Proft F. Computation of the hardness and the problem of negative electron affinities in density functional theory. Journal of Physical Chemistry A, 2005, 109(39): 8923–8929

[27] Doll K, Saunders V R, Harrison N M. Analytical hartree-fock gradients for periodic systems. International Journal of Quantum Chemistry, 2001, 82(1): 1–13

[28] Groth P, Baxter R M, Sletten J, Nielsen P H, Lindberg A A, Jansen G, Lamm B, Samuelsson B. Crystal structure of 3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexa-oxacyclononane (“Trimeric acetone peroxide”). Acta Chemica Scandinavica, 1969, 23(4): 1311– 1329

[29] Gelalcha F G, Schulze B, Lönnecke P. 3,3,6,6-Tetramethyl-1,2,4,5-tetroxane: A twinned crystal structure. Acta Crystallographica. Section C, Crystal Structure Communications, 2004, 60(3): 180–182

[30] Murray J S, Concha M C, Politzer P. Links between surface electrostatic potentials of energetic molecules, impact sensitivities and c-no2/n-no2 bond dissociation energies. Molecular Physics, 2009, 107(1): 89–97

[31] Rice B M, Pai S V, Hare J. Predicting heats of formation of energetic materials using quantum mechanical calculations. Combustion and Flame, 1999, 118(3): 445–458

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.

RIGHTS & PERMISSIONS

2014 Higher Education Press and Springer-Verlag Berlin Heidelberg