Performance of Twelve Density Functional Theory Methods in the Characterization of Three Trivalent Uranium Complexes
文献类型：期刊论文
| 作者 | Ding, WJ; Fang, WH; Chai ZF(柴之芳) ; Wang DQ(王东琪); Chai, ZF; Wang, DQ
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| 刊名 | ACTA PHYSICO-CHIMICA SINICA
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| 出版日期 | 2015 |
| 卷号 | 31期号:7页码:1283-1301 |
| 关键词 | Density functional theory Trivalent uranium complex Computational actinide chemistry QTAIM |
| 其他题名 | 采用12种密度泛函理论方法表征三种三价铀复合物 |
| 通讯作者 | 王东琪 |
| 英文摘要 | 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*)(2)U-eta(1)-CH2Ph (Cpd2) were used i.e., (Tp*)(2)U-eta(1)-CH2Ph (Cpd2), (Tp*)(2)U-kappa(2)-O2CCH2Ph (Cpd3), and (Tp*)(2)U-kappa(2)-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 OFT 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 high-valent 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. |
| 学科主题 | Chemistry |
| 类目[WOS] | Chemistry, Physical |
| 收录类别 | SCI |
| WOS记录号 | WOS:000358399500008 |
| 公开日期 | 2016-05-03 |
| 源URL | [http://ir.ihep.ac.cn/handle/311005/228582]  |
| 专题 | 高能物理研究所_院士 |
| 推荐引用方式 GB/T 7714 | Ding, WJ,Fang, WH,Chai ZF,et al. Performance of Twelve Density Functional Theory Methods in the Characterization of Three Trivalent Uranium Complexes[J]. ACTA PHYSICO-CHIMICA SINICA,2015,31(7):1283-1301. |
| APA | Ding, WJ,Fang, WH,柴之芳,王东琪,Chai, ZF,&Wang, DQ.(2015).Performance of Twelve Density Functional Theory Methods in the Characterization of Three Trivalent Uranium Complexes.ACTA PHYSICO-CHIMICA SINICA,31(7),1283-1301. |
| MLA | Ding, WJ,et al."Performance of Twelve Density Functional Theory Methods in the Characterization of Three Trivalent Uranium Complexes".ACTA PHYSICO-CHIMICA SINICA 31.7(2015):1283-1301. |
入库方式： OAI收割
来源：高能物理研究所
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