Journal article
Structure and dynamics of the molten alkali-chloride salts from an X-ray, simulation, and rate theory perspective
Physical chemistry chemical physics : PCCP, Vol.22(40), pp.22900-22917
2020
DOI: 10.1039/D0CP03672B
PMID: 32845262
Abstract
Molten salts are of great interest as alternative solvents, electrolytes, and heat transfer fluids in many emerging technologies. The macroscopic properties of molten salts are ultimately controlled by their structure and ion dynamics at the microscopic level and it is therefore vital to develop an understanding of these at the atomistic scale. Herein, we present high-energy X-ray scattering experiments combined with classical and ab initio molecular dynamics simulations to elucidate structural and dynamical correlations across the family of alkali-chlorides. Computed structure functions and transport properties are in reasonably good agreement with experiments providing confidence in our analysis of microscopic properties based on simulations. For these systems, we also survey different rate theory models of anion exchange dynamics in order to gain a more sophisticated understanding of the short-time correlations that are likely to influence transport properties such as conductivity. The anion exchange process occurs on the picoseconds time scale at 1100 K and the rate increases in the order KCl < NaCl < LiCl, which is in stark contrast to the ion pair dissociation trend in aqueous solutions. Consistent with the trend we observe for conductivity, the cationic size/mass, as well as other factors specific to each type of rate theory, appear to play important roles in the anion exchange rate trend.
Details
- Title: Subtitle
- Structure and dynamics of the molten alkali-chloride salts from an X-ray, simulation, and rate theory perspective
- Creators
- Santanu Roy - Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, USAFei Wu - Department of Chemistry, The University of Iowa, USAHaimeng Wang - Department of Chemical and Biomolecular Engineering, University of Notre Dame, USAAlexander S Ivanov - Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, USAShobha Sharma - Department of Chemistry, The University of Iowa, USAPhillip Halstenberg - Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, USA, Department of ChemistrySimerjeet K Gill - Nuclear Science and Technology Department, Brookhaven National Lab, USAA. M Milinda Abeykoon - National Synchrotron Light Source II (NSLS-II), Brookhaven National Lab, USAGihan Kwon - National Synchrotron Light Source II (NSLS-II), Brookhaven National Lab, USAMehmet Topsakal - Nuclear Science and Technology Department, Brookhaven National Lab, USABobby Layne - Chemistry Division, Brookhaven National Lab, USAKotaro Sasaki - Chemistry Division, Brookhaven National Lab, USAYong Zhang - Department of Chemical and Biomolecular Engineering, University of Notre Dame, USAShannon M Mahurin - Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, USASheng Dai - Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, USA, Department of ChemistryClaudio J Margulis - Department of Chemistry, The University of Iowa, USAEdward J Maginn - Department of Chemical and Biomolecular Engineering, University of Notre Dame, USAVyacheslav S Bryantsev - Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, USA
- Resource Type
- Journal article
- Publication Details
- Physical chemistry chemical physics : PCCP, Vol.22(40), pp.22900-22917
- DOI
- 10.1039/D0CP03672B
- PMID
- 32845262
- NLM abbreviation
- Phys Chem Chem Phys
- ISSN
- 1463-9076
- eISSN
- 1463-9084
- Grant note
- DOI: 10.13039/100000015, name: U.S. Department of Energy, award: DE-AC05-00OR22725, DE-SC0012704, DEAC05-00OR22725, DESC0012704
- Language
- English
- Date published
- 2020
- Academic Unit
- Chemistry
- Record Identifier
- 9984216673302771
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