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Published February 7, 2015 | Supplemental Material + Published
Journal Article Open

Initial decomposition reaction of di-tetrazine-tetroxide (DTTO) from quantum molecular dynamics: implications for a promising energetic material


Di-tetrazine-tetroxide (DTTO) was predicted in 2001 to have a density (up to 2.3 g cm^(−3)) and heat of detonation (up to 421.0 kcal mol^(−1)) better than other explosives, making it the "holy grail" of energetic materials (EMs), but all attempts at synthesis have failed. We report Density Functional Theory (DFT) molecular dynamics simulations (DFT-MD) on DTTO crystal for the two most stable monomers. We predict that the most stable isomer (c1) has a density of ρ = 1.96 g cm^(−3) with an estimated detonation velocity (D_v) of 9.70 km s^(−1) and a detonation pressure (D_p) of 43.0 GPa, making it comparable to RDX (ρ = 1.82 g cm^(−3), D_v = 8.75 km s^(−1), D_p = 35.0 GPa), HMX (ρ = 1.91 g cm^(−3), D_v = 9.10 km s^(−1), D_p = 39.3 GPa) and CL-20 (ρ = 2.04 g cm^(−3), D_v = 9.38 km s^(−1), D_p = 44.1 GPa). The DFT-MD studies find that the initial reaction at lower pressure is unimolecular decomposition to form two N_2O molecules (barrier 45.9 kcal mol^(−1)), while at higher pressure it is intermolecular oxygen-transfer with a barrier of 40.1 kcal mol^(−1). For the c2 isomer (less stable by 1.2 kcal mol^(−1)) the initial reaction involves two DTTO molecules reacting to form a dimer which then releases N_2 as a direct product (barrier 48.1 kcal mol^(−1)), a unique initial reaction among EMs. These results suggest that DTTO may have a higher thermal stability (barrier >7.0 kcal mol^(−1) higher) than RDX, HMX, and CL-20.

Additional Information

© 2014 The Royal Society of Chemistry. Received 23rd October 2014. Accepted 12th November 2014. First published online 25 Nov 2014. We thank Dr Cliff Bedford and Dr Al Stern for suggesting the importance of this work. All computations were carried out on the Army HPC systems; we thank Betsy Rice and Larry Davis for assistance. Personnel were supported mostly by ONR (N00014-09-1-0634, Cliff Bedford), with some assistance from ARO (W911NF-05-1-0345 and W911NF-08-1-0124). C.-C. Ye was sponsored by the China Scholarship Council (CSC), and thanks the Innovation Project for Postgraduates in Universities of Jiangsu Province (Grant no. CXZZ13_0213).

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