CPMD investigation of α-RDX and ε-CL-20: the transition of deflagration to detonation depending on the self-produced radicals
Literature Information
Tiantian Zhang, Longjiu Cheng, Jianguo Zhang, Kun Wang
1,3,5-Trinitroperhydro-1,3,5-triazine (RDX) and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) are the classic high energy nitramine compounds. Herein, we performed simulations of the overall decomposition pathways of condensed α-RDX and ε-CL-20 by applying the Car–Parrinello molecular dynamics (CPMD) method. Both of them appear to have similar distinct initial decomposition pathways, which are the bond cleavages of N–NO2 bonds. Interestingly, we find that the continuous explosion is nonspontaneous without the participation of self-produced hydrogen radicals of RDX or oxygen radicals of CL-20. Increased radicals are produced gradually with increasing temperature, which activates further entropy-increased steps, resulting in the uncontrollable transition of deflagration to detonation with the formation of NOx, COx and HCN. Herein, we provide a detailed and systematic description of the decomposition for unit-cell α-RDX and ε-CL-20 under increased temperature, which can be summarized as C3H6O6N6 (RDX) → NO + HNO + H2 + CO2 + HCHO + HNCN + N2O and C6H6O12N12 (CL-20) → NO + HONO + 5HCN + CO2 + N2O + 3NO2.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.









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