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采用紫外光电子能谱(PES)和量子化学方法,研究了以CFCl3化合物为代表的系列化合物(CFCl3、CF2Cl2、CF3Cl、CCl4)不同离子态的电子结构和性质。结果表明,四种化合物CF3Cl、CF2Cl2、CFCl3、CCl4的第一电离能依次下降。结合从头算自洽场分子轨道(abinitioSCFMO)和外壳层格林函数法(OVGF)计算对化合物的PES进行了分析和指认,表明化合物的外层轨道中Cl的孤对电子成分对电离能存在明显的影响;外层格林函数法计算得到电离能与实验吻合很好;同时发现在外壳层格林函数法计算结果中由于考虑相关能,得到的分子轨道存在能级顺序的交错。
The electronic structures and properties of different ionic states of CFCl3, CFCl3, CF2Cl2, CF3Cl and CCl4 were studied by UV-Vis spectroscopy and quantum chemistry methods. The results show that the four compounds CF3Cl, CF2Cl2, CFCl3, CCl4 the first ionization energy in turn decreased. Combined with ab initio SCFMO and OVGF calculations, the PES of the compounds was analyzed and assigned to indicate that the lone pair of electrons in the outer orbit of the compound has a significant effect on the ionization energy The results show that the ionospheric energy calculated by the Outer Green’s function method is in good agreement with the experimental data. At the same time, it is found that the order of the energy levels of the molecular orbitals obtained by the Green’s function method in the outer shell is staggered.