臭氧氧化偏二甲肼生成二甲基亚硝胺的量子化学计算

利用量子化学密度泛函理论(DFT)的B3LYP方法,对臭氧氧化偏二甲肼(UDMH)生成二甲基亚硝胺(DMNA)过程中相关的反应机理进行了理论研究;优化了各个反应物、中间体、过渡态及产物的分子构型,对其进行了能量分析及反应路径跟踪。结果表明,UDMH首先被氧化为中间体1,1-二甲基二氮烯,然后中间体再被氧化生成DMNA,计算得到上述两步反应的反应热分别为97.53kJ/mol和217.74kJ/mol,反应极易进行,通过能量数据能够预测生成DMNA的可能的反应历程。

Quantum Chemical Calculation of Forming N-nitrosodimethylamine in the Oxidation of Unsymmetrical Dimethylhydrazine by Ozone

Using density functional theory (DFT)-B3LYP method,the theoretical study on the correlative reaction mechanism of forming N-nitrosodimethylamine (DMNA) in the oxidation process of unsymmetrical dimethylhydrazine(UDMH)by ozone was performed.The molecular configurations of various reactants,transition states,intermediates and products were optimized.The energy analysis and tracking of reaction path were carried out.The results show that UDMH is firstly oxidized into an intermediate named 1,1-dimethyldiazene,and then the intermediate is oxidized into DMNA.The reaction heat of the two steps reaction obtained by calculated is 97.53 and 217.74 kJ/mol,respectively.The reaction is easy to carry out.According to the energy data,the probable reaction mechanism of DMNA generation can be predicted.