Density functional theory (DFT) is a widely used computational method for predicting the physical and chemical properties of metals and organometals. As the number of electrons and orbitals in an atom increases, DFT calculations for actinide complexes become more demanding due to increased complexity. Moreover, reasonable levels of theory for calculating the structures of actinide complexes are not extensively studied. In this study, 38 calculations, based on various combinations, were performed on molecules containing two representative actinides to determine the optimal combination for predicting the geometries of actinide complexes. Among the 38 calculations, four optimal combinations were identified and compared with experimental data. The optimal combinations were applied to a more complicated and practical actinide compound, the uranyl complex (UO2(2,2'-(1E,1'E)-(2,2-dimethylpropane-1,3-dyl)bis(azanylylidene)(CH3OH)), for further confirmation. The corresponding optimal calculation combination provides a reasonable level of theory for accurately optimizing the structure of actinide complexes using DFT.
Keywords: DFT; actinides; americium (III) hexachloride; uranium hexafluoride; uranyl complex.