Elucidating Ionic Correlations beyond Simple Charge Alternation in Molten MgCl2-KCl Mixtures

Fei Wu; Santanu Roy; Alexander S. Ivanov; Simerjeet K. Gill; Mehmet Topsakal; Eric Dooryhee; Milinda Abeykoon; Gihan Kwon; Leighanne C. Gallington; Phillip Halstenberg; Bobby Layne; Yoshiki Ishii; Shannon M. Mahurin; Sheng Dai; Vyacheslav S. Bryantsev; Claudio J. Margulis

doi:10.1021/acs.jpclett.9b02845

Elucidating Ionic Correlations beyond Simple Charge Alternation in Molten MgCl₂-KCl Mixtures

Fei Wu, Santanu Roy, Alexander S. Ivanov, Simerjeet K. Gill, Mehmet Topsakal, Eric Dooryhee, Milinda Abeykoon, Gihan Kwon, Leighanne C. Gallington, Phillip Halstenberg, Bobby Layne, Yoshiki Ishii, Shannon M. Mahurin, Sheng Dai, Vyacheslav S. Bryantsev, Claudio J. Margulis

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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 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. An analysis of the coordination structure for Mg²⁺ ions paints a more complex picture than previously understood, with multiple accessible states of distinct geometries.

Original language	English
Pages (from-to)	7603-7610
Number of pages	8
Journal	Journal of Physical Chemistry Letters
Volume	10
Issue number	24
DOIs	https://doi.org/10.1021/acs.jpclett.9b02845
State	Published - Dec 19 2019

Funding

This work was supported as part of the Molten Salts in Extreme Environments Energy Frontier Research Center, funded by the U.S. Department of Energy Office of Science. BNL and ORNL are operated under DOE contracts DE-SC0012704 and DE-AC05-00OR22725, respectively. This research used resources of the Advanced Photon Source operated by Argonne National Laboratory under Contract No. DE-AC02-06CH11357, and the X-ray Pair Distribution Function (PDF; 28-ID-1) beamline of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704 and of the Oak Ridge Leadership Computing Facility at the Oak Ridge National Laboratory supported by the Office of Science of the U.S. Department of Energy under contract No. DE-AC05-00OR22725. Y.I. was supported by a Grant-in-Aid for JSPS Fellows (Grant No. JP17J01006) from the Japan Society for the Promotion of Science. F.W. and C.J.M. also acknowledge the University of Iowa High Performance Computing Facility.

Funders	Funder number
28-ID-1
DOE Office of Science
JSPS Fellows
Molten Salts in Extreme Environments Energy Frontier Research Center
National Synchrotron Light Source II
Oak
Office of Science User Facility operated
U.S. Department of Energy
Office of Science
Argonne National Laboratory	DE-AC02-06CH11357
Argonne National Laboratory
Oak Ridge National Laboratory
Brookhaven National Laboratory	DE-SC0012704
Brookhaven National Laboratory
Savannah River Operations Office, U.S. Department of Energy
Japan Society for the Promotion of Science	17J01006
Japan Society for the Promotion of Science

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10.1021/acs.jpclett.9b02845

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Wu, F., Roy, S., Ivanov, A. S., Gill, S. K., Topsakal, M., Dooryhee, E., Abeykoon, M., Kwon, G., Gallington, L. C., Halstenberg, P., Layne, B., Ishii, Y., Mahurin, S. M., Dai, S., Bryantsev, V. S., & Margulis, C. J. (2019). Elucidating Ionic Correlations beyond Simple Charge Alternation in Molten MgCl₂-KCl Mixtures. Journal of Physical Chemistry Letters, 10(24), 7603-7610. https://doi.org/10.1021/acs.jpclett.9b02845

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title = "Elucidating Ionic Correlations beyond Simple Charge Alternation in Molten MgCl2-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 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. An analysis of the coordination structure for Mg2+ ions paints a more complex picture than previously understood, with multiple accessible states of distinct geometries.",

author = "Fei Wu and Santanu Roy and Ivanov, {Alexander S.} and Gill, {Simerjeet K.} and Mehmet Topsakal and Eric Dooryhee and Milinda Abeykoon and Gihan Kwon and Gallington, {Leighanne C.} and Phillip Halstenberg and Bobby Layne and Yoshiki Ishii and Mahurin, {Shannon M.} and Sheng Dai and Bryantsev, {Vyacheslav S.} and Margulis, {Claudio J.}",

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doi = "10.1021/acs.jpclett.9b02845",

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Wu, F, Roy, S , Ivanov, AS, Gill, SK, Topsakal, M, Dooryhee, E, Abeykoon, M, Kwon, G, Gallington, LC, Halstenberg, P, Layne, B, Ishii, Y, Mahurin, SM , Dai, S , Bryantsev, VS & Margulis, CJ 2019, 'Elucidating Ionic Correlations beyond Simple Charge Alternation in Molten MgCl₂-KCl Mixtures', Journal of Physical Chemistry Letters, vol. 10, no. 24, pp. 7603-7610. https://doi.org/10.1021/acs.jpclett.9b02845

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AU - Wu, Fei

AU - Roy, Santanu

AU - Ivanov, Alexander S.

AU - Gill, Simerjeet K.

AU - Topsakal, Mehmet

AU - Dooryhee, Eric

AU - Abeykoon, Milinda

AU - Kwon, Gihan

AU - Gallington, Leighanne C.

AU - Halstenberg, Phillip

AU - Layne, Bobby

AU - Ishii, Yoshiki

AU - Mahurin, Shannon M.

AU - Dai, Sheng

AU - Bryantsev, Vyacheslav S.

AU - Margulis, Claudio J.

PY - 2019/12/19

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N2 - 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. An analysis of the coordination structure for Mg2+ ions paints a more complex picture than previously understood, with multiple accessible states of distinct geometries.

AB - 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. 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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Elucidating Ionic Correlations beyond Simple Charge Alternation in Molten MgCl₂-KCl Mixtures

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