CH3ONO 与 Br 自由基反应的机理研究

摘要

Abatract:Using B3LYP method of quantum chemistry, Br free radicals and CH3 ONO reaction mechanism was studied on the 6-311++g( d,p) basis set level, optimization of the reaction on the geometrical configuration of reactant, transition state and product was optimized.On the basis of the BLYP/6-311++g(d,p) optimization configuration, each point of energy in the aqueous solution was detected by using the CPCM configuration.The results showed that Br free radical and CH3 ONO had three kinds of reaction mechanism.First kind was Br free radical mechanism of CH3 seized, the second one was Br free radical addition to CH3 ONO methoxy O atoms on eliminating NO addition elimination mechanism, the third one was Br free radical mechanism of H direct extraction.%运用量子化学B3LYP方法，在6－311＋＋g（ d，p）基组水平上研究Br自由基和CH3 ONO的反应机理，优化得到了反应途径上反应物、过渡态和产物的几何构型；在B3LYP／6－311＋＋g（ d，p）优化的构型基础上，以CPCM模型得到了其在水溶液中各点的能量。研究结果表明：Br自由基与CH3 ONO有3种反应机制。第1种是Br自由基加成到CH3 ONO分子C原子上消除NO2的机制，第2种是Br自由基加成到CH3 ONO分子甲氧基O原子上消除NO的加成－消除机制，第3种是Br自由基对H直接夺取的机制。