Understanding the Structure and Thermal Stability of Cs3UCl6(s) in the CsCl-UCl3 System

Aiswarya Padinhare Manissery; Juliano Schorne-Pinto; Yunping Zhoujin; Annabelle Husek; Ronald E. Booth; Jack A. Wilson; Gopabandhu Panigrahi; Hunter B. Tisdale; Dmitry S. Maltsev; Alexander S. Ivanov; Phillip W. Halstenberg; Sheng Dai; Hans Conrad zur Loye; Theodore M. Besmann

doi:10.1021/acs.inorgchem.6c00471

Understanding the Structure and Thermal Stability of Cs₃UCl₆(s) in the CsCl-UCl₃ System

Aiswarya Padinhare Manissery
, Juliano Schorne-Pinto
, Yunping Zhoujin
, Annabelle Husek
, Ronald E. Booth
, Jack A. Wilson
, Gopabandhu Panigrahi
, Hunter B. Tisdale
, Dmitry S. Maltsev
, Alexander S. Ivanov
, Phillip W. Halstenberg
, Sheng Dai
, Hans Conrad zur Loye
, Theodore M. Besmann

Research output: Contribution to journal › Article › peer-review

Abstract

The present effort details the first synthesis and structural characterization of Cs3UCl6(s), a compound for which no crystallographic information has previously been reported, despite its significance in the thermochemical evaluation of the CsCl-UCl3 system. The compound was synthesized by a solid-state reaction and characterized by powder X-ray diffraction (XRD) with Rietveld refinement, with its purity analyzed by ICP-MS and oxygen quantified by inert gas fusion analysis. The phase crystallizes in a monoclinic unit cell (space group C2/c) with lattice parameters a = 27.303(11) Å, b = 8.204(3) Å, and c = 13.386(5) Å. The thermal stability of this compound was investigated by high-temperature XRD, which indicated a possible low-temperature polymorphic transformation. The structural information reported here resolves a long-standing deficiency in the crystallographic description of the CsCl–UCl3 system and provides a robust reference for thermochemical assessments. Moreover, the accurate thermal characterization of Cs3UCl6(s) has broader implications for actinide science, particularly in high-temperature molten salt systems, where cesium and uranium chlorides coexist.

Original language	English
Pages (from-to)	7098-7103
Number of pages	6
Journal	Inorganic Chemistry
Volume	65
Issue number	13
DOIs	https://doi.org/10.1021/acs.inorgchem.6c00471
State	Published - Apr 6 2026

Funding

The authors gratefully acknowledge Dr. Pandu Wisesa for his valuable assistance with the DFT calculations during the revision of the manuscript. This research was supported by the U.S. Department of Energy Office of Nuclear Energy, Nuclear Energy University Programs under award DE-NE0009386. ORNL is operated under DOE contract number DE-AC05-00OR22725, and the work at UTK and ORNL was supported as part of the Molten Salts in Extreme Environments (MSEE) Energy Frontier Research Center, funded by the DOE Office of Science, Basic Energy Sciences.

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Padinhare Manissery, A., Schorne-Pinto, J., Zhoujin, Y., Husek, A., Booth, R. E., Wilson, J. A., Panigrahi, G., Tisdale, H. B., Maltsev, D. S., Ivanov, A. S., Halstenberg, P. W., Dai, S., zur Loye, H. C., & Besmann, T. M. (2026). Understanding the Structure and Thermal Stability of Cs₃UCl₆(s) in the CsCl-UCl₃ System. Inorganic Chemistry, 65(13), 7098-7103. https://doi.org/10.1021/acs.inorgchem.6c00471

@article{359d93839a214a52af2219bd3abe08cd,

title = "Understanding the Structure and Thermal Stability of Cs3UCl6(s) in the CsCl-UCl3 System",

abstract = "The present effort details the first synthesis and structural characterization of Cs3UCl6(s), a compound for which no crystallographic information has previously been reported, despite its significance in the thermochemical evaluation of the CsCl-UCl3 system. The compound was synthesized by a solid-state reaction and characterized by powder X-ray diffraction (XRD) with Rietveld refinement, with its purity analyzed by ICP-MS and oxygen quantified by inert gas fusion analysis. The phase crystallizes in a monoclinic unit cell (space group C2/c) with lattice parameters a = 27.303(11) {\AA}, b = 8.204(3) {\AA}, and c = 13.386(5) {\AA}. The thermal stability of this compound was investigated by high-temperature XRD, which indicated a possible low-temperature polymorphic transformation. The structural information reported here resolves a long-standing deficiency in the crystallographic description of the CsCl–UCl3 system and provides a robust reference for thermochemical assessments. Moreover, the accurate thermal characterization of Cs3UCl6(s) has broader implications for actinide science, particularly in high-temperature molten salt systems, where cesium and uranium chlorides coexist.",

author = "\{Padinhare Manissery\}, Aiswarya and Juliano Schorne-Pinto and Yunping Zhoujin and Annabelle Husek and Booth, \{Ronald E.\} and Wilson, \{Jack A.\} and Gopabandhu Panigrahi and Tisdale, \{Hunter B.\} and Maltsev, \{Dmitry S.\} and Ivanov, \{Alexander S.\} and Halstenberg, \{Phillip W.\} and Sheng Dai and \{zur Loye\}, \{Hans Conrad\} and Besmann, \{Theodore M.\}",

note = "Publisher Copyright: {\textcopyright} 2026 American Chemical Society",

year = "2026",

month = apr,

day = "6",

doi = "10.1021/acs.inorgchem.6c00471",

language = "English",

volume = "65",

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journal = "Inorganic Chemistry",

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Padinhare Manissery, A, Schorne-Pinto, J, Zhoujin, Y, Husek, A, Booth, RE, Wilson, JA, Panigrahi, G, Tisdale, HB, Maltsev, DS, Ivanov, AS, Halstenberg, PW , Dai, S, zur Loye, HC & Besmann, TM 2026, 'Understanding the Structure and Thermal Stability of Cs₃UCl₆(s) in the CsCl-UCl₃ System', Inorganic Chemistry, vol. 65, no. 13, pp. 7098-7103. https://doi.org/10.1021/acs.inorgchem.6c00471

TY - JOUR

T1 - Understanding the Structure and Thermal Stability of Cs3UCl6(s) in the CsCl-UCl3 System

AU - Padinhare Manissery, Aiswarya

AU - Schorne-Pinto, Juliano

AU - Zhoujin, Yunping

AU - Husek, Annabelle

AU - Booth, Ronald E.

AU - Wilson, Jack A.

AU - Panigrahi, Gopabandhu

AU - Tisdale, Hunter B.

AU - Maltsev, Dmitry S.

AU - Ivanov, Alexander S.

AU - Halstenberg, Phillip W.

AU - Dai, Sheng

AU - zur Loye, Hans Conrad

AU - Besmann, Theodore M.

PY - 2026/4/6

Y1 - 2026/4/6

N2 - The present effort details the first synthesis and structural characterization of Cs3UCl6(s), a compound for which no crystallographic information has previously been reported, despite its significance in the thermochemical evaluation of the CsCl-UCl3 system. The compound was synthesized by a solid-state reaction and characterized by powder X-ray diffraction (XRD) with Rietveld refinement, with its purity analyzed by ICP-MS and oxygen quantified by inert gas fusion analysis. The phase crystallizes in a monoclinic unit cell (space group C2/c) with lattice parameters a = 27.303(11) Å, b = 8.204(3) Å, and c = 13.386(5) Å. The thermal stability of this compound was investigated by high-temperature XRD, which indicated a possible low-temperature polymorphic transformation. The structural information reported here resolves a long-standing deficiency in the crystallographic description of the CsCl–UCl3 system and provides a robust reference for thermochemical assessments. Moreover, the accurate thermal characterization of Cs3UCl6(s) has broader implications for actinide science, particularly in high-temperature molten salt systems, where cesium and uranium chlorides coexist.

AB - The present effort details the first synthesis and structural characterization of Cs3UCl6(s), a compound for which no crystallographic information has previously been reported, despite its significance in the thermochemical evaluation of the CsCl-UCl3 system. The compound was synthesized by a solid-state reaction and characterized by powder X-ray diffraction (XRD) with Rietveld refinement, with its purity analyzed by ICP-MS and oxygen quantified by inert gas fusion analysis. The phase crystallizes in a monoclinic unit cell (space group C2/c) with lattice parameters a = 27.303(11) Å, b = 8.204(3) Å, and c = 13.386(5) Å. The thermal stability of this compound was investigated by high-temperature XRD, which indicated a possible low-temperature polymorphic transformation. The structural information reported here resolves a long-standing deficiency in the crystallographic description of the CsCl–UCl3 system and provides a robust reference for thermochemical assessments. Moreover, the accurate thermal characterization of Cs3UCl6(s) has broader implications for actinide science, particularly in high-temperature molten salt systems, where cesium and uranium chlorides coexist.

UR - https://www.scopus.com/pages/publications/105035024981

U2 - 10.1021/acs.inorgchem.6c00471

DO - 10.1021/acs.inorgchem.6c00471

M3 - Article

C2 - 41860346

AN - SCOPUS:105035024981

SN - 0020-1669

VL - 65

SP - 7098

EP - 7103

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 13

ER -

Understanding the Structure and Thermal Stability of Cs₃UCl₆(s) in the CsCl-UCl₃ System

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