We employed cryogenic X-ray Raman spectroscopy to investigate the early-stage decomposition of the high explosive molecule hexanitrohexaazaisowurtzitane (CL-20). By systematically varying the radiation dose under cryogenic conditions, we induced the decomposition of the molecule using ionizing radiation and observed the evolution of spectral features at the carbon, nitrogen, and oxygen K edges. Through extensive first-principles calculations, we identified key intermediates in the early stages of the decomposition process, resulting from C–C and C–N bond cleavage which leads to the opening of the internal cage structure. A detailed analysis of spectral trends and fingerprints provided evidence supporting N–NO 2 homolytic cleavage as the primary initial decomposition pathway. The combination of advanced core-level spectroscopy methods and state-of-the-art theoretical calculations enabled a comprehensive characterization of the molecular changes induced by controlled radiation dose exposures. Our findings establish a benchmark for understanding the decomposition chemistry of high-explosive materials, offering important insights into their stability and reactivity under extreme conditions.

中文翻译：

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用低温 X 射线拉曼光谱破译烈性炸药的分解途径

我们采用低温 X 射线拉曼光谱研究高爆炸分子六硝基六氮杂异喔兹烷 （CL-20） 的早期分解。通过在低温条件下系统地改变辐射剂量，我们利用电离辐射诱导分子分解，并观察碳、氮和氧 K 边缘光谱特征的演变。通过广泛的第一性原理计算，我们确定了分解过程早期阶段的关键中间体，这些中间体是由 C-C 和 C-N 键裂解引起的，导致内部笼状结构的打开。对光谱趋势和指纹图谱的详细分析提供了支持 N-NO 2 均解裂解作为主要初始分解途径的证据。先进的核心级光谱方法与最先进的理论计算相结合，能够全面表征受控辐射剂量暴露引起的分子变化。我们的研究结果为理解高爆炸材料的分解化学建立了基准，为了解它们在极端条件下的稳定性和反应性提供了重要见解。