High energy barrier hydroxyl radical dissociation mechanism of a low shock sensitivity dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (TKX-50) explosive

As a representative of the new generation of high-energy explosives, TKX-50 has attracted widespread attention due to its remarkably low sensitivity toward shock. However, the reported decomposition barriers of TKX-50 (∼37 kcal mol⁻¹) are comparable to those of commonly used explosives. The mechanism of its low shock sensitivity remains unclear. In this study, using an ab initio molecular dynamics method combined with a multiscale shock simulation technique and transition state calculations (at the B2PLYP-D3/Def2TZVP level), we discovered an unconventional reaction pathway of TKX-50 under shock, and its rate-controlling step is the dissociation of the hydroxyl radical (OH) from the anion ring after proton transfer, followed by ring rupture and the production of H₂O and N₂. The barrier for this OH dissociation reaction is as high as 51.9 kcal mol⁻¹. In contrast, under thermal stimuli, TKX-50 prefers to open rings directly after proton transfer without losing the OH. The corresponding barrier is 35.4 kcal mol⁻¹, which is in good agreement with previous studies. The reason for the unconventional reaction pathway of TKX-50 under shock may be the suppression of anion ring opening in thermal decomposition by steric hindrance upon shock compression. In addition, the dominant N₂ generation pathway under shock releases less energy than pyrolysis which further explains the low shock sensitivity of TKX-50. This study comprehensively elucidates the different reaction mechanisms of TKX-50 under thermal and shock conditions and proposes a crucial reaction pathway leading to its low shock sensitivity. These findings will contribute to the understanding and application of tetrazole anionic energetic salts.