Elucidating Ionic Correlations Beyond Simple Charge Alternation in Molten MgCl2–KCl Mixtures

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.

doi:10.1021/acs.jpclett.9b02845

Title: Elucidating Ionic Correlations Beyond Simple Charge Alternation in Molten MgCl₂–KCl Mixtures

Journal Article · 17 November 2019 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.9b02845 · OSTI ID:1593246

Wu, Fei ^[1];

^[2];

^[2]; Gill, Simerjeet K. ^[3]; Topsakal, Mehmet ^[3]; Dooryhee, Eric ^[4]; Abeykoon, Milinda ^[4];

^[4];

^[5];

^[6]; Layne, Bobby ^[3];

^[7];

^[2];

^[1]

Univ. of Iowa, Iowa City, IA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Argonne National Lab. (ANL), Argonne, IL (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Osaka Univ. (Japan)

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.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Energy Frontier Research Centers (EFRC) (United States). Molten Salts in Extreme Environments (MSEE); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704; AC05-00OR22725; AC02-06CH11357

OSTI ID:: 1593246

Report Number(s):: BNL--213564-2020-JAAM

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 24 Vol. 10; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Elucidating Ionic Correlations Beyond Simple Charge Alternation in Molten MgCl2–KCl Mixtures

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Title: Elucidating Ionic Correlations Beyond Simple Charge Alternation in Molten MgCl₂–KCl Mixtures