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含能材料  2005 

四硝基四氮杂双环辛烷气相热解引发机理

Keywords: 物理化学,四硝基四氮杂双环辛烷,热解机理,活化能,热力学参数,动力学参数

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Abstract:

运用量子化学中非限制性Hartree-Fock自洽场PM3(UHF-SCF-PM3)分子轨道(MO)方法计算研究了四硝基四氮杂双环辛烷的气相热解引发反应,求得可能的三种不同热解途径的反应过渡态、活化能和位能曲线,揭示了反应中键级、分子几何和原子电荷的递变规律。发现标题物与通常的硝胺类爆炸物遵循类似的热解引发反应机理,皆始于N—NO2键的均裂,生成两个自由基。基于统计热力学方法和Eyring的绝对反应速率理论求得该反应的热力学和动力学参数。

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