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Main Authors: Wadehra, Anubhav, Chahal, Rajni, Banerjee, Shubhojit, Levy, Alexander, Zhang, Yifan, Yan, Haoxuan, Olds, Daniel, Zhong, Yu, Pal, Uday, Lam, Stephen, Ludwig, Karl
Format: Preprint
Published: 2024
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Online Access:https://arxiv.org/abs/2403.06049
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author Wadehra, Anubhav
Chahal, Rajni
Banerjee, Shubhojit
Levy, Alexander
Zhang, Yifan
Yan, Haoxuan
Olds, Daniel
Zhong, Yu
Pal, Uday
Lam, Stephen
Ludwig, Karl
author_facet Wadehra, Anubhav
Chahal, Rajni
Banerjee, Shubhojit
Levy, Alexander
Zhang, Yifan
Yan, Haoxuan
Olds, Daniel
Zhong, Yu
Pal, Uday
Lam, Stephen
Ludwig, Karl
contents The local atomic structure of NaF-ZrF$_4$ (53-47 mol%) molten system and its evolution with temperature are examined with x-ray scattering measurements and compared with $ab-initio$ and Neural Network-based molecular dynamics (NNMD) simulations in the temperature range 515-700 °C. The machine-learning enhanced NNMD calculations offer improved efficiency while maintaining accuracy at higher distances compared to ab-initio calculations. Looking at the evolution of the Pair Distribution Function with increasing temperature, a fundamental change in the liquid structure within the selected temperature range, accompanied by a slight decrease in overall correlation is revealed. NNMD calculations indicate the co-existence of three different fluorozirconate complexes: [ZrF$_6$]$^{2-}$, [ZrF$_7$]$^{3-}$, and [ZrF$_8$]$^{4-}$, with a temperature-dependent shift in the dominant coordination state towards a 6-coordinated Zr ion at 700°C. The study also highlights the metastability of different coordination structures, with frequent interconversions between 6 and 7 coordinate states for the fluorozirconate complex from 525 °C to 700 °C. Analysis of the Zr-F-Zr angular distribution function reveals the presence of both $"$edge-sharing$"$ and $"$corner-sharing$"$ fluorozirconate complexes with specific bond angles and distances in accord with previous studies, while the next-nearest neighbor cation-cation correlations demonstrate a clear preference for unlike cations as nearest-neighbor pairs, emphasizing non-random arrangement. These findings contribute to a comprehensive understanding of the complex local structure of the molten salt, providing insights into temperature-dependent preferences and correlations within the molten system.
format Preprint
id arxiv_https___arxiv_org_abs_2403_06049
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle X-ray and molecular dynamics study of the temperature-dependent structure of molten NaF-ZrF4
Wadehra, Anubhav
Chahal, Rajni
Banerjee, Shubhojit
Levy, Alexander
Zhang, Yifan
Yan, Haoxuan
Olds, Daniel
Zhong, Yu
Pal, Uday
Lam, Stephen
Ludwig, Karl
Materials Science
The local atomic structure of NaF-ZrF$_4$ (53-47 mol%) molten system and its evolution with temperature are examined with x-ray scattering measurements and compared with $ab-initio$ and Neural Network-based molecular dynamics (NNMD) simulations in the temperature range 515-700 °C. The machine-learning enhanced NNMD calculations offer improved efficiency while maintaining accuracy at higher distances compared to ab-initio calculations. Looking at the evolution of the Pair Distribution Function with increasing temperature, a fundamental change in the liquid structure within the selected temperature range, accompanied by a slight decrease in overall correlation is revealed. NNMD calculations indicate the co-existence of three different fluorozirconate complexes: [ZrF$_6$]$^{2-}$, [ZrF$_7$]$^{3-}$, and [ZrF$_8$]$^{4-}$, with a temperature-dependent shift in the dominant coordination state towards a 6-coordinated Zr ion at 700°C. The study also highlights the metastability of different coordination structures, with frequent interconversions between 6 and 7 coordinate states for the fluorozirconate complex from 525 °C to 700 °C. Analysis of the Zr-F-Zr angular distribution function reveals the presence of both $"$edge-sharing$"$ and $"$corner-sharing$"$ fluorozirconate complexes with specific bond angles and distances in accord with previous studies, while the next-nearest neighbor cation-cation correlations demonstrate a clear preference for unlike cations as nearest-neighbor pairs, emphasizing non-random arrangement. These findings contribute to a comprehensive understanding of the complex local structure of the molten salt, providing insights into temperature-dependent preferences and correlations within the molten system.
title X-ray and molecular dynamics study of the temperature-dependent structure of molten NaF-ZrF4
topic Materials Science
url https://arxiv.org/abs/2403.06049