论文部分内容阅读
HNO和CH_2O可在λ_(EXC)≥645nm和λ_(EXC)=345 nm的光照射下,生成顺式和反式亚硝基甲醇。对于这个光反应,实验工作者提出了两种机理。本文用ab initio方法(STO-3G基组),通过求得反应的S_0、S_1和T_1态的过渡态及反应途径(IRC),并用GUGA CI方法(基于图形酉群理论的CI方法)计算能量,支持了实验提出的两种机理之一,即在两种入射光照射下,第一步都生成反式亚硝基甲醇,在λ_(EXC)≥645nm的入射光继续照射下,第一步生成的反应产物光异构化为顺式的机理。
HNO and CH_2O can generate cis- and trans-nitroso-methanol under irradiation of λ_ (EXC) ≥645nm and λ_ (EXC) = 345nm. For this photoreaction, experimenters have proposed two mechanisms. In this paper, the ab initio method (STO-3G basis set) was used to calculate the transition states and reaction pathways (IRC) of the S_0, S_1 and T_1 states and the GUGA CI method (CI method based on the graphic unitary group theory) , Which supports one of the two mechanisms proposed in the experiment. In the first step, trans-nitrosylmethanol is generated under the irradiation of two incident lights. When the incident light of λ_ (EXC) ≥645 nm continues to be irradiated, the first step The resulting reaction product is photoisomerized into a cis-mechanism.