Pu(H2O)53+和Pu(H2O)54+ 团簇的相对论密度泛函研究

用TPSSTPSS密度泛函方法, Pu离子和H₂O分子分别采用相对论有效原子实势(RECP)和6-31g基组, 研究了Pu(H₂O)₅³⁺和Pu(H₂O)₅⁴⁺ 团簇溶剂化和非溶剂化效应中的几何结构及紫外可见吸收光谱. 计算结果表明: 水溶剂环境对Pu(H₂O)₅³⁺及Pu(H₂O)₅⁴⁺ 团簇的几何结构影响都比较明显. NBO电荷分析表明水分子与钚离子之间没有直接的电荷转移. 所研究团簇的未配对电子都占据5f轨道. 在气相及水溶剂环境下, 所研究团簇的紫外可见吸收光谱存在较大差距. 主要的吸收峰大都源于f电子之间的跃迁.

The relativistic density functional study of Pu(H2O)53+and Pu(H2O)54+ cluster

The geometry and Uv-vis absorption spectroscopy study of Pu(H₂O)₅³⁺ and Pu(H₂O)₅⁴⁺ cluster in the gas phase and aqueous solvent are listed in this paper, which use the TPSSTPSS density functional method with the relativistic effective core potential (RECP) for Pu ion and 6-31g basis set for H₂O molecules. The calculation results show that the geometrical structure of Pu(H₂O)₅³⁺ and Pu(H₂O)₅⁴⁺ cluster have significant change in the aqueous solvent environment compared with the geometry in the gas phase. The NBO charge analysisshows that the direct charge transfer does not happen between water molecules and plutonium ion. And the unpaired electrons occupy 5f orbital in the research clusters. The Uv-visible absorption spectrum of the research clusters is obviously different in gas phase and aqueous solvent. And the main absorption peaks mostly come from the transition of f electronic .