Serving as energetic plasticizer, revealing the aging mechanisms and kinetics of bis(2,2-dinitropropyl) formal is helpful to remove the safety hazards. Here, based on the DFT barrier of methylene-H abstraction by nitro group (HONO elimination) and the continuous reaction model, an experimentally comparable half-life of BDNPF is reported by transition state theory simulation. Rather than the HONO elimination-addition reactions, HONO bimolecular decompositions are preferred, where the energetically preferred pathway involves formation of NO, and generation of NO and HNO catalyzed by HONO. Interestingly, newly reported transition state bifurcations lower the barriers and accelerate HONO decomposition, which also leads to the rate constant of generating HNO consistent with experiments. Moreover, HNO undertakes hydrogen transferred bimolecular pathway and HONO-catalyzed pathway to decompose into NO and HO. This work clarifies the degradation pathways and species, and is helpful to the deep understanding of the aging procedures of energetic materials.

中文翻译：

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过渡态分岔和HONO催化促进双(2,2二硝基丙基)缩甲醛的老化机制和动力学


作为含能增塑剂，揭示双(2,2-二硝基丙基)缩甲醛的老化机理和动力学有助于消除其安全隐患。在这里，基于硝基（HONO消除）抽象亚甲基-H的DFT势垒和连续反应模型，通过过渡态理论模拟报告了实验上可比较的BDNPF半衰期。与 HONO 消除-加成反应不同，HONO 双分子分解是优选的，其中能量上优选的途径涉及 NO 的形成以及 HONO 催化的 NO 和 HNO 的生成。有趣的是，新报道的过渡态分岔降低了势垒并加速了 HONO 分解，这也导致生成 HNO 的速率常数与实验一致。此外，HNO通过氢转移双分子途径和HONO催化途径分解为NO和H2O。该工作阐明了含能材料的降解途径和种类，有助于深入理解含能材料的老化过程。