Acta Phys. -Chim. Sin. ›› 2015, Vol. 31 ›› Issue (7): 1283-1301.doi: 10.3866/PKU.WHXB201504291


Performance of Twelve Density Functional Theory Methods in the Characterization of Three Trivalent Uranium Complexes

DING Wan-Jian1, FANG Wei-Hai1, CHAI Zhi-Fang2,3, WANG Dong-Qi2   

  1. 1 Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875, P. R. China;
    2 CAS Key Laboratory of Nuclear Radiation and Nuclear Energy Techniques, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, P. R. China;
    3 School of Radiation Medicine and Interdisciplinary Sciences (RAD-X), Soochow University, Suzhou 215123, Jiangsu Province, P. R. China
  • Received:2015-01-07 Revised:2015-04-29 Published:2015-07-08
  • Contact: DING Wan-Jian, WANG Dong-Qi;
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21073013, 91026000, 91226105) and Chinese Academy of Sciences Hundred Talent Program (Y2291810S3).


We report a comparative study on the characterization of three trivalent uranium complexes using 12 density functional theory (DFT) methods, i.e., BP86, PBE, B3LYP, B3PW91, BHandHLYP, PBE0, X3LYP, CAM-B3LYP, TPSS, M06L, M06, and M06-2X, representing (meta-)GGA and hybrid (meta-)GGA levels of treatment of molecular systems. The MP2 method was used in single-point calculations to provide an ab initio view of the electronic structure. Three model systems in the experimental work on the activation of CO2 and CS2 by a trivalent uranium complex (Tp*)2U-η1-CH2Ph (Cpd2) were used i.e., (Tp*)2U-η1-CH2Ph (Cpd2), (Tp*)2U-κ2- O2CCH2Ph (Cpd3), and (Tp*)2U-κ2-S2CCH2Ph (Cpd4) (Tp=hydrotris(3, 5-dimethylpyrazolyl)borate). The hybrid functionals, B3LYP and B3PW91, displayed good performance in view of both the geometrical and electronic structures. The MP2 method generated consistent results as DFT methods for Cpd2 and Cpd3, while provided an odd picture of the electronic structure of Cpd4 that may be due to its single determinant feature, leading to its capture of an electronic configuration of Cpd4 different from the one with the DFT methods. The use of a quasi-relativistic 5f-in-core ECP (LPP) treatment for U(III) in the thermodynamic calculations was supported by the calculations with a small-core ECP treatment (SPP) for U. Owing to increasing interests in low-valent actinide molecular systems, this work complements previous comparative studies, which mainly focus on highvalent actinide complexes, and provides timely information on the performance of 12 widely used DFT methods in studying low-valent actinide systems. It is expected to contribute to a more sensible selection of DFT methods in the study of low-valent actinide molecular systems.

Key words: Density functional theory, Trivalent uranium complex, Computational actinide chemistry, QTAIM


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