期刊
JOURNAL OF COMPUTATIONAL CHEMISTRY
卷 43, 期 19, 页码 1286-1297出版社
WILEY
DOI: 10.1002/jcc.26933
关键词
AMOEBA force field parameterization; concentrations of divalent chloride salts; divalent lanthanides; molecular dynamics simulations; water exchange time
资金
- Office of Science [DE-FG02-13ER16414]
In this work, the hydration of Sm2+ and Eu2+ cations were studied using AMOEBA force fields. The coordination numbers obtained were in good agreement with experimental results, and the decrease in coordination number of Ln(2+) compared with Ln(3+) was attributed to progressive water exchange events. The effects of chloride counter anions on the coordination of Ln(2+) cations were also investigated.
The chemistry of divalent lanthanides, Ln(2+), is a growing sub-field of heavy element chemistry owing to new synthetic approaches. However, some theoretical aspects of these unusual cations are currently underdeveloped, especially as they relate to their dynamic properties in solution. In this work, we address the hydration of two of the classical Ln(2+) cations, Sm2+ and Eu2+, using atomic multipole optimized energetic for biomolecular applications (AMOEBA) force fields. These cations have not been parameterized to date with AMOEBA, and few studies are available because of their instability with respect to oxidation in aqueous media. Coordination numbers (CN's) of 8.2 and 8.1 respectively for Sm2+ and Eu2+, and 8.8 for both Sm3+ and Eu3+ have been obtained and are in good agreement with the few available AIMD and X-ray absorption fine structures studies. The decreased CN of Ln(2+) compared with Ln(3+) arises from progressive water exchange events that indicates the gradual stabilization of 8-coordinate structures with respect to 9-coordinate geometries. Moreover, the effects of the chloride counter anions on the coordination of Ln(2+) cations have been studied at different chloride concentrations in this work. Lastly, water exchange times of Ln(2+) cations have been calculated to provide a comprehensive understanding of the behavior of Eu2+ and Sm2+ in aqueous chloride media.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据