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Theoretical investigation on the mechanism and dynamics of oxo exchange of neptunyl(VI) hydroxide in aqueous solution
Yang X(杨霞); Chai ZF(柴之芳); Wang DQ(王东琪); Yang, X; Chai, ZF; Wang, DQ
刊名PHYSICAL CHEMISTRY CHEMICAL PHYSICS
2015
卷号17期号:11页码:7537-7547
学科分类Chemistry; Physics
DOI10.1039/c4cp04586f
通讯作者杨霞 ; 王东琪
文章类型Article
英文摘要Four types of reaction mechanisms for the oxo ligand exchange of monomeric and dimeric neptunyl(VI) hydroxide in aqueous solution were explored computationally using density functional theory (DFT) and ab initio classical molecular dynamics. The obtained results were compared with previous studies on the oxo exchange of uranyl hydroxide, as well as with experiments. It is found that the stable T-shaped [NpO3(OH)(3)](3-) intermediate is a key species for oxo exchange in the proton transfer in mononuclear Path I and binuclear Path IV, similar to the case of uranyl(VI) hydroxide. Path I is thought to be the preferred oxo exchange mechanism for neptunyl(VI) hydroxide in our calculations, due to the lower activation energy (22.7 and 13.1 kcal mol(-1) for Delta H-double dagger and Delta H-double dagger, respectively) of the overall reaction. Path II via a cis-neptunyl structure assisted by a water molecule might be a competitive channel against Path I with a mononuclear mechanism, owing to a rapid dynamical process occurring in Path II. In Path IV with the binuclear mechanism, oxo exchange is accomplished via the interaction between [NpO2(OH)(4)](2-) and T-shaped [NpO3(OH)(3)](3-) with a low activation energy for the rate-determining step, however, the overall energy required to fulfill the reaction is slightly higher than that in mononuclear Path I, suggesting a possible binuclear process in the higher energy region. The chemical bonding evolution along the reaction pathways was discussed by using topological methodologies of the electron localization function (ELF).
类目[WOS]Chemistry, Physical ; Physics, Atomic, Molecular & Chemical
收录类别SCI ; CA ; MEDLINE
WOS记录号WOS:000351436400046
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文献类型期刊论文
条目标识符http://ir.ihep.ac.cn/handle/311005/228280
专题院士_期刊论文
中国科学院高能物理研究所_多学科研究中心
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Yang X,Chai ZF,Wang DQ,et al. Theoretical investigation on the mechanism and dynamics of oxo exchange of neptunyl(VI) hydroxide in aqueous solution[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2015,17(11):7537-7547.
APA 杨霞,柴之芳,王东琪,Yang, X,Chai, ZF,&Wang, DQ.(2015).Theoretical investigation on the mechanism and dynamics of oxo exchange of neptunyl(VI) hydroxide in aqueous solution.PHYSICAL CHEMISTRY CHEMICAL PHYSICS,17(11),7537-7547.
MLA 杨霞,et al."Theoretical investigation on the mechanism and dynamics of oxo exchange of neptunyl(VI) hydroxide in aqueous solution".PHYSICAL CHEMISTRY CHEMICAL PHYSICS 17.11(2015):7537-7547.
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