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

doi:10.3866/PKU.WHXB201504291

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	Performance of Twelve Density Functional Theory Methods in the Characterization of Three Trivalent Uranium Complexes
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
	Ding, WJ; Fang, WH; Chai ZF(柴之芳); Wang DQ(王东琪); Chai, ZF; Wang, DQ
	2015
发表期刊	ACTA PHYSICO-CHIMICA SINICA
卷号	31 期号:7 页码:1283-1301
通讯作者	王东琪
文章类型	Article
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.
关键词	Density functional theory Trivalent uranium complex Computational actinide chemistry QTAIM
学科领域	Chemistry
DOI	10.3866/PKU.WHXB201504291
收录类别	SCI
WOS类目	Chemistry, Physical
WOS记录号	WOS:000358399500008
引用统计
文献类型	期刊论文
条目标识符	http://ir.ihep.ac.cn/handle/311005/228582
专题	院士多学科研究中心
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.

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