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采用UHF,CIS和CASSCF方法,在aug-cc-pvdz基组水平上对CH2=CClF?h?v→?CH=CClF+H的光解反应通道及其后续反应作了研究.计算表明:分子吸收一个光子后,在第一电子激发态(S1)经过一个过渡态解离与Cl原子同侧的C—H键,这与用CIS方法计算垂直激发得到的π→σ*C-H跃迁及其对Frank-Condon点的计算中分子的单占轨道和键电荷密度变化所预测的结果是一致的.光解产物?CH=CClF(基态)还可再发生反应,经过渡态解离C—Cl键或是C—F键.
The photolysis reaction channels of CH2 = CClF? H? V?? CH = CClF + H and their subsequent reactions were studied at the aug-cc-pvdz basis by UHF, CIS and CASSCF methods. After absorbing one photon, the C-H bond on the same side of the Cl atom is dissociated in a transition state in the first electron-excited state (S1), which is in good agreement with the calculation by the CIS method for the π → σ * CH transition obtained by vertical excitation and The calculations for the Frank-Condon point are consistent with the predicted single charge orbitals and the changes in the charge density of the bond. The photolytic product CH = CClF (ground state) can also re-react, leaving the C-Cl bond Or C-F key.