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采用密度泛函理论(DFT),在B3LYP/RECP/6-31G(d,p)水平对U(Ⅵ)、U(Ⅳ)、Np(Ⅳ)、Pu(Ⅳ)与乙异羟肟酸(AHA)摩尔比为1∶1和1∶2配合物的结构和热力学参数进行了研究。结构计算发现,M-O键键长随原子序数增加而减短,对配合物进行自然轨道分析(NBO)发现,M和AHA的摩尔比为1∶1的配合物中M-O键是明显的离子键,共价成分很少,在1∶2配合物中M-O键共价成分增加。对配位反应的热力学参数进行计算发现,金属离子与AHA配合物的稳定性依次为Pu(Ⅳ)>Np(Ⅳ)>U(Ⅳ)>U(Ⅵ),理论计算结果与实验测量得到的稳定常数顺序一致。
The effects of U (Ⅵ), U (Ⅳ), Np (Ⅳ), Pu (Ⅳ) and acetohydroxamic acid (Ⅵ) at B3LYP / RECP / 6-31G (d, p) AHA) molar ratio of 1: 1 and 1: 2 structure and thermodynamic parameters were studied. Structural calculations showed that the bond length of MO bonds decreased with the increase of atomic number. Natural complex orbital analysis (NBO) showed that the MO bond in the complex with M and AHA molar ratio of 1: 1 was obviously ionic bond, Few covalent components in the 1: 2 MO bond covalent component increases. The thermodynamic parameters of the coordination reaction were calculated and found that the stability of the metal ion and AHA complexes in turn was Pu (Ⅳ)> Np (Ⅳ)> U (Ⅳ)> U (Ⅵ), the theoretical calculation results and experimental measurements Stability constant in the same order.