Structural and Thermodynamic Properties of the CmIII Ion Solvated by Water and Methanol

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• 作者：Morgan P. Kelley ; Ping Yang ; Sue B. Clark ; Aurora E. Clark
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：May 16, 2016
• 年：2016
• 卷：55
• 期：10
• 页码：4992-4999
• 全文大小：430K
• 年卷期：0
• ISSN：1520-510X

文摘

The geometric and electronic structures of the 9-coordinate Cm³⁺ ion solvated with both water and methanol are systematically investigated in the gas phase at each possible solvent-shell composition and configuration using density functional theory and second-order Møller–Plesset perturbation theory. Ab initio molecular dynamics simulations are employed to assess the effects of second and third solvent shells on the gas-phase structure. The ion–solvent dissociation energy for methanol is greater than that of water, potentially because of increased charge donation to the ion made possible by the electron-rich methyl group. Further, the ion–solvent dissociation energy and the ion–solvent distance are shown to be dependent on the solvent-shell composition. This has implications for solvent exchange, which is generally the rate-limiting step in complexation reactions utilized in the separation of curium from complex metal mixtures that derive from the advanced nuclear fuel cycle.