Cp_4An和COT_2An(Cp^-=C_5H_5^-,COT^(2-)=C_8H_8^(2-),An=U(Ⅳ),Pu(Ⅳ))的结构和光谱性质的密度泛函理论研究  

DFT Studies on Structure and Spectral Properties of Organoactinide Complexes of Cp_4An and COT_2An(Cp^-=C_5H_5^-, COT^(2-)=C_8H_8^(2-), An=U(Ⅳ), Pu(Ⅳ))

作　　者：辜家芳[1] 许可[2] 陈文凯[3] 

机构地区：[1]福州大学至诚学院化学工程系,福州350002 [2]闽江学院,福州350108 [3]福州大学化学系,福州350108

出　　处：《无机化学学报》2017年第9期1579-1586,共8页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.10676007)资助项目;福建省教育厅科研基金(No.JB14222)资助项目

摘　　要：采用密度泛函理论研究气相和四氢呋喃(THF)溶剂中Cp4An和COT2An(Cp-=C5H5-,COT2-=C8H82-,An=U(Ⅳ),Pu(Ⅳ))配合物的性质。THF溶剂对配合物的溶剂化效应采用类导体极化连续模型(CPCM)近似计算。计算结果显示在THF溶液中各配合物结合能的大小顺序为COT2Pu>COT2U>Cp4Pu>Cp4U。溶剂化效应降低了该金属有机配合物的结合能。计算得到的化合物的结构参数和红外光谱数据与实验数据保持一致。通过对Cp4An和COT2An(An=U(Ⅳ),Pu(Ⅳ))的分子轨道能级图分析发现,采用最高的RSC ECP赝势计算COT2U和Cp4U的基态分别为三重fφ2和fσ2组态;而COT2Pu和Cp4Pu的基态分别为五重fσ1fπ1fφ2和fσ3fδ1组态。Properties of Cp4An and COT2An （Cp-=C5H5^-, COT2-=C8H8^2-, An=U（Ⅳ）, Pu（Ⅳ）） species both in gas phase and tetrahydrofuran （THF） solution are systematically studied by DFT （density functional theory）. The solvent effect of THF is simulated by a conductor-like polarized continuum model （CPCM）. Theoretical calculations show that the binding energies of the complexes are in the order of COT2Pu〉COT2U〉Cp4Pu〉Cp4U. Solvent effects decreased binding energies of the structures. The optimized geometry structures and the IR spectra for the complexes in gas and aqueous phase are in accordance to the available experimental data very well. Detail studies on MO energy levels for Cp4An and COT：An with An=U（Ⅳ）, Pu（Ⅳ） calculated with rsc ecp indicate that COT2U and CP4U favors triplets f2 and f2 configuration respectively, meanwhile, COT2Pu and Cp4Pu favor quintets fσ^1fπ^1fφ^2 and fσ^3fδ^1 configuration respectively.

关 键 词：金属有机物 铀 钚 密度泛函理论 溶剂化效应 

分 类 号：O641[理学—物理化学]