4.5 Article

Unraveling Local Structure of Molten Salts via X-ray Scattering, Raman Spectroscopy, and Ab Initio Molecular Dynamics

期刊

JOURNAL OF PHYSICAL CHEMISTRY B
卷 125, 期 22, 页码 5971-5982

出版社

AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcb.1c03786

关键词

-

资金

  1. Molten Salts in Extreme Environments (MSEE) Energy Frontier Research Center - U.S. Department of Energy Office of Science
  2. Brookhaven National Laboratory (BNL)
  3. DOE [DE-SC0012704, DE-AC05-00OR22725]
  4. Deutsche Forschungsgemeinschaft (DFG) [Br 5494/1-1]
  5. Office of Science of the U.S. Department of Energy [DE-AC05-00OR22725, DE-AC02-05CH11231]
  6. Argonne National Laboratory [DE-AC0206CH11357]

向作者/读者索取更多资源

By employing a multimodal approach and theoretical modeling, researchers in this work successfully resolved issues concerning the local structure of molten MgCl2. They demonstrated the reliability of AIMD simulations in achieving excellent agreement between experimental and simulated spectra, providing structural insights not directly available from experiments alone.
In this work, we resolve a long-standing issue concerning the local structure of molten MgCl2 by employing a multimodal approach, including X-ray scattering and Raman spectroscopy, along with the theoretical modeling of the experimental spectra based on ab initio molecular dynamics (AIMD) simulations utilizing several density functional theory (DFT) methods. We demonstrate the reliability of AIMD simulations in achieving excellent agreement between the experimental and simulated spectra for MgCl2 and 50 mol % MgCl2 + 50 mol % KCl, and ZnCl2, thus allowing structural insights not directly available from experiment alone. A thorough computational analysis using five DFT methods provides a convergent view that octahedrally coordinated magnesium in pure MgCl2 upon melting preferentially coordinates with five chloride anions to form distorted square pyramidal polyhedra that are connected via corners and to a lesser degree via edges. This is contrasted with the results for ZnCl2, which does not change its tetrahedral coordination on melting. Although the five-coordinate MgCl53- complex was not considered in the early literature, together with an increasing tendency to form a tetrahedrally coordinated complex with decreasing the MgCl2 content in the mixture with alkali metal chloride systems, current work reconciles the results of most previous seemingly contradictory experimental studies.

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。

评论

主要评分

4.5
评分不足

次要评分

新颖性
-
重要性
-
科学严谨性
-
评价这篇论文

推荐

暂无数据
暂无数据