Coupling effects of high temperature and pressure on the decomposition mechanisms of 1,1‐diamino‐2,2‐dinitroehethe crystal: Ab initio molecular dynamics simulations

Recently, Dreger et al. experimentally investigated the phase diagram and decomposition of 1,1‐diamino‐2,2‐dinitroethene (FOX‐7) single crystal compressed hydrostatically up to 10 GPa and heated over a range of 293–750 K (J. Phys. Chem. C 2016, 120, 11092–11098). As a continuation, we performed ab initio molecular dynamic simulations to study the initiation mechanisms and subsequent decomposition of FOX‐7 at a temperature of 504 K (initial decomposition temperature) coupled with a pressure of 1–5 GPa, 604 K at 5GPa, and 704 K at 5 GPa. However, our two compressing ways are different: the former is static hydrostatical compression, while our way is dynamic compression. Our results indicate that the initial decomposition mechanism was dependent on the temperature but independent of the pressure. The initial decomposition step is the bimolecular intermolecular hydrogen transfer. The subsequent decomposition of FOX‐7 is sensitive to both the temperature and pressure. At 504 K, the decomposition of FOX‐7 was accelerated from 1 to 2 GPa and from 3 to 5 GPa but decelerated from 2 to 3 GPa. The temperature exhibits a positive effect on the decomposition. Overall, the temperature and pressure have great cooperative effects on the decomposition of FOX‐7. Our study may provide new insight into understanding the initial mechanisms and decomposition reactions of energetic materials at relatively low temperatures coupled with different pressures in atomic detail. We performed ab initio molecular dynamic simulations to study the decomposition of FOX‐7 at different temperatures coupled with different pressures. The initial decomposition mechanism is the intermolecular hydrogen transfer, dependent on the temperature but independent of the pressure. The subsequent decomposition of FOX‐7 is sensitive to both the temperature and pressure. The temperature exhibits a positive effect on the decomposition.