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Title: Elucidating Ionic Correlations Beyond Simple Charge Alternation in Molten MgCl 2–KCl Mixtures

Abstract

The development of technologies for nuclear reactors based on molten salts has seen a big resurgence. The success of thermodynamic models for these hinges in part on our ability to predict at the atomistic level the behavior of pure salts and their mixtures under a range of conditions. In this letter, we present high-energy X-ray scattering experiments and molecular dynamics simulations that describe the molten structure of mixtures of MgCl 2 and KCl. As one would expect, KCl is a prototypical salt in which structure is governed by simple charge alternation. In contrast, MgCl 2 and its mixtures with KCl display more complex correlations including intermediate-range order and the formation of Cl -decorated Mg 2+ chains. A thorough computational analysis suggests that intermediate-range order beyond charge alternation may be traced to correlations between these chains. Here, an analysis of the coordination structure for Mg 2+ ions paints a more complex picture than previously understood, with multiple accessible states of distinct geometries.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2];  [3];  [3];  [3];  [3]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5];  [3]; ORCiD logo [6]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Iowa, Iowa City, IA (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
  6. Osaka Univ. (Japan)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division; USDOE Office of Science (SC), Nuclear Physics (NP) (SC-26)
OSTI Identifier:
1593246
Alternate Identifier(s):
OSTI ID: 1593254
Report Number(s):
BNL-213564-2020-JAAM; BNL-213557-2020-JAAM
Journal ID: ISSN 1948-7185
Grant/Contract Number:  
SC0012704; AC05-00OR22725; AC02-06CH11357; JP17J01006
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 10; Journal Issue: 24; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 73 NUCLEAR PHYSICS AND RADIATION PHYSICS

Citation Formats

Wu, Fei, Roy, Santanu, Ivanov, Alexander S., Gill, Simerjeet K., Topsakal, Mehmet, Dooryhee, Eric, Abeykoon, Milinda, Kwon, Gihan, Gallington, Leighanne C., Halstenberg, Phillip, Layne, Bobby, Ishii, Yoshiki, Mahurin, Shannon M., Dai, Sheng, Bryantsev, Vyacheslav S., and Margulis, Claudio J. Elucidating Ionic Correlations Beyond Simple Charge Alternation in Molten MgCl2–KCl Mixtures. United States: N. p., 2019. Web. doi:10.1021/acs.jpclett.9b02845.
Wu, Fei, Roy, Santanu, Ivanov, Alexander S., Gill, Simerjeet K., Topsakal, Mehmet, Dooryhee, Eric, Abeykoon, Milinda, Kwon, Gihan, Gallington, Leighanne C., Halstenberg, Phillip, Layne, Bobby, Ishii, Yoshiki, Mahurin, Shannon M., Dai, Sheng, Bryantsev, Vyacheslav S., & Margulis, Claudio J. Elucidating Ionic Correlations Beyond Simple Charge Alternation in Molten MgCl2–KCl Mixtures. United States. doi:10.1021/acs.jpclett.9b02845.
Wu, Fei, Roy, Santanu, Ivanov, Alexander S., Gill, Simerjeet K., Topsakal, Mehmet, Dooryhee, Eric, Abeykoon, Milinda, Kwon, Gihan, Gallington, Leighanne C., Halstenberg, Phillip, Layne, Bobby, Ishii, Yoshiki, Mahurin, Shannon M., Dai, Sheng, Bryantsev, Vyacheslav S., and Margulis, Claudio J. Mon . "Elucidating Ionic Correlations Beyond Simple Charge Alternation in Molten MgCl2–KCl Mixtures". United States. doi:10.1021/acs.jpclett.9b02845.
@article{osti_1593246,
title = {Elucidating Ionic Correlations Beyond Simple Charge Alternation in Molten MgCl2–KCl Mixtures},
author = {Wu, Fei and Roy, Santanu and Ivanov, Alexander S. and Gill, Simerjeet K. and Topsakal, Mehmet and Dooryhee, Eric and Abeykoon, Milinda and Kwon, Gihan and Gallington, Leighanne C. and Halstenberg, Phillip and Layne, Bobby and Ishii, Yoshiki and Mahurin, Shannon M. and Dai, Sheng and Bryantsev, Vyacheslav S. and Margulis, Claudio J.},
abstractNote = {The development of technologies for nuclear reactors based on molten salts has seen a big resurgence. The success of thermodynamic models for these hinges in part on our ability to predict at the atomistic level the behavior of pure salts and their mixtures under a range of conditions. In this letter, we present high-energy X-ray scattering experiments and molecular dynamics simulations that describe the molten structure of mixtures of MgCl2 and KCl. As one would expect, KCl is a prototypical salt in which structure is governed by simple charge alternation. In contrast, MgCl2 and its mixtures with KCl display more complex correlations including intermediate-range order and the formation of Cl–-decorated Mg2+ chains. A thorough computational analysis suggests that intermediate-range order beyond charge alternation may be traced to correlations between these chains. Here, an analysis of the coordination structure for Mg2+ ions paints a more complex picture than previously understood, with multiple accessible states of distinct geometries.},
doi = {10.1021/acs.jpclett.9b02845},
journal = {Journal of Physical Chemistry Letters},
number = 24,
volume = 10,
place = {United States},
year = {2019},
month = {11}
}

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This content will become publicly available on November 18, 2020
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