二氯卡宾与异氰酸反应机理的量子化学研究
孔超;韩彦霞;陈东平;高立国;耿志远
【期刊名称】《原子与分子物理学报》 【年(卷),期】2011(028)005
【摘要】The reaction mechanism of singlet and triplet CC12 with HNCO has been investigated by B3LYP method of density function theory. The geometries and harmonic of reactants, intermediates, transition states and products have been calculated at the B3LYP/6-311 ++G\level. Intermediates and transition states were confirmed by the results of vibration analysis and the IRC calculation. The energies of stationary point were calculated at G3 level. The results indicate that the reaction of singlet CCU with HNCO have O-atom abstraction channel* insert N-H channel, NH abstraction channel, and triplet CC12 with HNCO has H-atom
abstraction
channel,
among
which
singlet
reaction
HNCO+CCl2→IM3 →TS2→P2 (QCljONH) was the main pathway with the lowest activation energy.%采用密度泛函理论B3LYP方法研究了单、三重态CCl2与HNCO的反应机理,在B3LYP/6-311++G”水平上对反应物,中间体,过渡态进行了全几何参数优化,通过频率分析和IRC确定中间体和过渡态,并用G3方法计算了各个驻点的单点能.计算结果表明:单重态的CCl2与HNCO的反应有抽提氧、插入N-H键、抽提亚氨基的路径,三重态的CC12与HNCO发生抽提氢的反应,其中单重态反应通道HNCO+CCl2→IM3→TS2→P2(C2Cl2ONH)反应能垒最低,为主反应通道.
二氯卡宾与异氰酸反应机理的量子化学研究
