Temperature and anion ligand field dependence of LnCl3 (Ln = Nd, Dy, Sm) electronic absorption spectra in LiCl–KCl eutectic molten salt

Moon, Jeremy; Fuller, Jon; An, Qi; Chidambaram, Dev

doi:10.1016/j.pnucene.2023.104584

Temperature and anion ligand field dependence of LnCl₃ (Ln = Nd, Dy, Sm) electronic absorption spectra in LiCl–KCl eutectic molten salt

Journal Article · Thu Feb 02 00:00:00 EST 2023 · Progress in Nuclear Energy

DOI:https://doi.org/10.1016/j.pnucene.2023.104584· OSTI ID:2418346

Moon, Jeremy ^[1]; Fuller, Jon ^[2]; An, Qi ^[2]; Chidambaram, Dev ^[2]

Univ. of Nevada, Reno, NV (United States); OSTI
Univ. of Nevada, Reno, NV (United States)

A comprehensive knowledge of the coordination, bonding, and speciation of elements in molten salt mixtures is necessary to understand and predict the chemical and physical properties of the salt. Absorption spectroscopy can yield information about the chemistry of species of interest in alkali halide molten salt mixtures by revealing information about the electronic structure and transitions of those species. In this study, ultraviolet (UV), visible (vis), and near-infrared (NIR) absorption spectroscopy was used to examine changes to the electronic structure of trivalent Nd, Sm, and Dy in LiCl–KCl eutectic molten salt with changes in temperature and the anion composition of the melt. With increasing temperature, changes to spectral features suggest a distortion of the coordination complexes. Changes to lineshape with the substitution of alternative halide anions were examined and analyzed, revealing differences in the coordination for I^– versus F^– with the lanthanides. Gaussian peak fitting was used to show that the changes in lineshape with the progressive addition of F^– anions can be explained by the superposition of a set of absorption bands from complexes with all Cl^– anion ligands and a set of blueshifted absorption bands from complexes containing both F^– and Cl^– anion ligands. Finally, this work yields a new method to analyze and interpret change to electronic absorption spectra for f-block elements dissolved in alkali halide molten salts as well as new observations of the interactions of larger and smaller halide anions with lanthanides in Cl^–-based molten salts.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Nevada, Reno, NV (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE); USDOE Office of Nuclear Energy (NE), Nuclear Energy University Program (NEUP); USNRC

Grant/Contract Number:: NE0008889

OSTI ID:: 2418346

Alternate ID(s):: OSTI ID: 1961898

Journal Information:: Progress in Nuclear Energy, Journal Name: Progress in Nuclear Energy Vol. 157; ISSN 0149-1970

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (44)

Coupling-constant dependence of atomization energies Ernzerhof, Matthias; Perdew, John P.; Burke, Kieron International Journal of Quantum Chemistry, Vol. 64, Issue 3 https://doi.org/10.1002/(SICI)1097-461X(1997)64:3<285::AID-QUA2>3.0.CO;2-S	journal	January 1997
Competitive Coordination of Chloride and Fluoride Anions Towards Trivalent Lanthanide Cations (La ³⁺ and Nd ³⁺ ) in Molten Salts Jiang, Shilin; Lan, Jianhui; Wang, Lin Chemistry – A European Journal, Vol. 27, Issue 45 https://doi.org/10.1002/chem.202101505	journal	July 2021
Photometric Method for the Quantification of Chlorophylls and Their Derivatives in Complex Mixtures: Fitting with Gauss-Peak Spectra Küpper, Hendrik; Spiller, Martin; Küpper, Frithjof C. Analytical Biochemistry, Vol. 286, Issue 2 https://doi.org/10.1006/abio.2000.4794	journal	November 2000
Quantitative analysis of trivalent uranium and lanthanides in a molten chloride by absorption spectrophotometry Fujii, Toshiyuki; Uda, Takeshi; Fukasawa, Kazuhito Journal of Radioanalytical and Nuclear Chemistry, Vol. 296, Issue 1 https://doi.org/10.1007/s10967-012-2008-3	journal	August 2012
Raman spectrum of the LaCl6−3 octahedron in molten and solid Cs2NaLaCl6, Cs3LaCl6 and K3LaCl6 Papatheodorou, G. N. Inorganic and Nuclear Chemistry Letters, Vol. 11, Issue 7-8 https://doi.org/10.1016/0020-1650(75)80021-3	journal	July 1975
Ab initio molecular dynamics for liquid metals Kresse, G. Journal of Non-Crystalline Solids, Vol. 192-193 https://doi.org/10.1016/0022-3093(95)00355-X	journal	December 1995
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Hypersensitivity in the electronic transitions of lanthanide and actinide complexes Henrie, D. E.; Fellows, R. L.; Choppin, G. R. Coordination Chemistry Reviews, Vol. 18, Issue 2 https://doi.org/10.1016/S0010-8545(00)82044-5	journal	February 1976
Electronic absorption spectra of lanthanides in a molten chloride Fujii, Toshiyuki; Moriyama, Hirotake; Yamana, Hajimu Journal of Alloys and Compounds, Vol. 351, Issue 1-2 https://doi.org/10.1016/S0925-8388(02)01081-2	journal	March 2003
Analyzing the effect of natural gas, nuclear energy and renewable energy on GDP and carbon emissions: A multi-variate panel data analysis Azam, Anam; Rafiq, Muhammad; Shafique, Muhammad Energy, Vol. 219 https://doi.org/10.1016/j.energy.2020.119592	journal	March 2021
The future of the nuclear industry reconsidered: Risks, uncertainties, and continued promise Kessides, Ioannis N. Energy Policy, Vol. 48 https://doi.org/10.1016/j.enpol.2012.05.008	journal	September 2012
Electronic absorption spectra of lanthanides in a molten chloride Fujii, Toshiyuki; Nagai, Takayuki; Sato, Nobuaki Journal of Alloys and Compounds, Vol. 393, Issue 1-2 https://doi.org/10.1016/j.jallcom.2004.10.013	journal	May 2005
Electronic absorption spectra of lanthanides in a molten chloride Fujii, Toshiyuki; Nagai, Takayuki; Uehara, Akihiro Journal of Alloys and Compounds, Vol. 441, Issue 1-2 https://doi.org/10.1016/j.jallcom.2006.09.113	journal	August 2007
Thermal analysis of projected molten salt compositions during FFTF and EBR-II used nuclear fuel processing Karlsson, Toni Y.; Fredrickson, Guy L.; Yoo, Tae-Sic Journal of Nuclear Materials, Vol. 520 https://doi.org/10.1016/j.jnucmat.2019.04.016	journal	July 2019
Safety assessment of molten salt reactors in comparison with light water reactors Elsheikh, Badawy M. Journal of Radiation Research and Applied Sciences, Vol. 6, Issue 2 https://doi.org/10.1016/j.jrras.2013.10.008	journal	October 2013
Temperature dependence of the f←f hypersensitive transitions of Ho3+ and Nd3+ in molten salt solvents and the structure of the LaCl3–KCl melts Chrissanthopoulos, A.; Papatheodorou, G. N. Journal of Molecular Structure, Vol. 782, Issue 2-3 https://doi.org/10.1016/j.molstruc.2005.08.003	journal	January 2006
Near-infrared spectra and molar absorption coefficients of trivalent lanthanides dissolved in molten LiCl–KCl eutectic Moon, Jeremy; Chidambaram, Dev Progress in Nuclear Energy, Vol. 152 https://doi.org/10.1016/j.pnucene.2022.104375	journal	October 2022
Absorption Spectra of Molten Fluoride Salts. Solutions of Praseodymium, Neodymium, and Samarium Fluoride in Molten Lithium Fluoride Young, J. P.; White, J. C. Analytical Chemistry, Vol. 32, Issue 12 https://doi.org/10.1021/ac60168a031	journal	November 1960
Refractive indexes of ionic melts Iwadate, Y.; Mochinaga, J.; Kawamura, K. The Journal of Physical Chemistry, Vol. 85, Issue 24 https://doi.org/10.1021/j150624a036	journal	November 1981
Local Coordination about La ³⁺ in Molten LaCl ₃ and Its Mixtures with Alkali Chlorides Okamoto, Yoshihiro; Suzuki, Shinichi; Shiwaku, Hideaki The Journal of Physical Chemistry A, Vol. 114, Issue 13 https://doi.org/10.1021/jp910637p	journal	March 2010
Absorption spectroscopy for the quantitative prediction of lanthanide concentrations in the 3LiCl–2CsCl eutectic at 723 K Schroll, Cynthia A.; Lines, Amanda M.; Heineman, William R. Analytical Methods, Vol. 8, Issue 43 https://doi.org/10.1039/C6AY01520D	journal	January 2016
Study on the degradation mechanism and pathway of benzene dye intermediate 4-methoxy-2-nitroaniline via multiple methods in Fenton oxidation process Guo, Ying; Xue, Qiang; Cui, Kangping RSC Advances, Vol. 8, Issue 20 https://doi.org/10.1039/C8RA00627J	journal	January 2018
Coordination and thermophysical properties of select trivalent lanthanides in LiCl–KCl Fuller, Jon; Moon, Jeremy; Zhang, Jing Physical Chemistry Chemical Physics, Vol. 24, Issue 21 https://doi.org/10.1039/D1CP03056F	journal	January 2022
Vibrational modes and structure of lanthanide fluoride–potassium fluoride binary melts LnF3–KF (Ln=La, Ce, Nd, Sm, Dy, Yb) Dracopoulos, V.; Gilbert, B.; Papatheodorou, G. N. Journal of the Chemical Society, Faraday Transactions, Vol. 94, Issue 17 https://doi.org/10.1039/a802812e	journal	January 1998
Vibrational modes and structures of lanthanide halide–alkali halide binary melts LnBr3–KBr (Ln=La, Nd, Gd) and NdCl3–ACl (A=Li, Na, K, Cs) Photiadis, G. M.; Brresen, B.; Papatheodorou, G. N. Journal of the Chemical Society, Faraday Transactions, Vol. 94, Issue 17 https://doi.org/10.1039/a802813c	journal	January 1998
Probing the structure of GdCl3–KCl melt mixtures by electronic absorption spectroscopy of the hypersensitive f←f transitions of Ho3+ and by Raman spectroscopy Chrissanthopoulos, A.; Papatheodorou, G. N. Physical Chemistry Chemical Physics, Vol. 2, Issue 16 https://doi.org/10.1039/b004227g	journal	January 2000
Luminescence and excitation spectra of Nd3+ in Cs2NaGdCl6 : NdCl 3? 6 Tanner, Peter A.; Quagliano, John; Richardson, Frederick S. Journal of the Chemical Society, Faraday Transactions, Vol. 87, Issue 11 https://doi.org/10.1039/ft9918701707	journal	January 1991
Charge-transfer spectra and some related phenomena Orgel, L. E. Quarterly Reviews, Chemical Society, Vol. 8, Issue 4 https://doi.org/10.1039/qr9540800422	journal	January 1954
Raman spectra of ionic liquids: Interpretation via computer simulation Madden, Paul A.; Wilson, Mark; Hutchinson, Francis The Journal of Chemical Physics, Vol. 120, Issue 14 https://doi.org/10.1063/1.1650831	journal	April 2004
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Optical spectra and crystal field analysis of Dy³⁺ in Cs₂NaDyCl₆ and Cs₂NaYCl₆: Dy³⁺(5 mol %) Foster, David R.; Richardson, F. S. The Journal of Chemical Physics, Vol. 82, Issue 3 https://doi.org/10.1063/1.448481	journal	February 1985
Optical spectra and crystal field analysis of Nd³⁺ in the cubic Cs₂NaYCl₆ host Foster, David R.; Richardson, F. S.; Schwartz, R. W. The Journal of Chemical Physics, Vol. 82, Issue 2 https://doi.org/10.1063/1.448535	journal	January 1985
Isotropic and anisotropic Raman scattering from molten LiCl–CsCl mixtures: Composition and temperature effects Papatheodorou, G. N.; Kalogrianitis, S. G.; Mihopoulos, T. G. The Journal of Chemical Physics, Vol. 105, Issue 7 https://doi.org/10.1063/1.472129	journal	August 1996
Structure of molten MCl3 systems from a polarizable ion simulation model Hutchinson, Francis; Rowley, Adrian J.; Walters, Malcolm K. The Journal of Chemical Physics, Vol. 111, Issue 5 https://doi.org/10.1063/1.479471	journal	August 1999
Electronic spectra and crystal-field analysis of DyCl^3- ₆ in elpasolite lattices Tanner, Peter A.; Jayasankar, C. K.; Richardson, Frederick S. Molecular Physics, Vol. 65, Issue 1 https://doi.org/10.1080/00268978800100841	journal	September 1988
Structure of molten trivalent metal chlorides studied by using neutron diffraction: the systems TbCl₃, YCl₃, HoCl₃and ErCl₃ Wasse, Jonathan C.; Salmon, Philip S. Journal of Physics: Condensed Matter, Vol. 11, Issue 47 https://doi.org/10.1088/0953-8984/11/47/313	journal	November 1999
Structure of molten lanthanum and cerium tri-halides by the method of isomorphic substitution in neutron diffraction Wasse, Jonathan C.; Salmon, Philip S. Journal of Physics: Condensed Matter, Vol. 11, Issue 6 https://doi.org/10.1088/0953-8984/11/6/004	journal	January 1999
Structure of molten trivalent metal bromides studied by using neutron diffraction: the systems DyBr ₃ , YBr ₃ , HoBr ₃ and ErBr ₃ Wasse, Jonathan C.; Salmon, Philip S.; Delaplane, Robert G. Journal of Physics: Condensed Matter, Vol. 12, Issue 46 https://doi.org/10.1088/0953-8984/12/46/302	journal	October 2000
Energy levels and hypersensitivity of samarium(III) in the elpasolite Cs₂NaSmCl₆ Faucher, Michèle D.; Tanner, Peter A. Journal of Physics: Condensed Matter, Vol. 18, Issue 37 https://doi.org/10.1088/0953-8984/18/37/009	journal	September 2006
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 78, Issue 7 https://doi.org/10.1103/PhysRevLett.78.1396	journal	February 1997
Physicochemical Properties of Lanthanide(III) Iodide Species Formed in and Above Molten Salts Chrissanthopoulos, A. ECS Proceedings Volumes, Vol. 2004-24, Issue 1 https://doi.org/10.1149/200424.0825PV	journal	January 2004
Development of Pyroprocessing and its Future Direction Inoue, Tadashi; Koch, Lothar Nuclear Engineering and Technology, Vol. 40, Issue 3 https://doi.org/10.5516/NET.2008.40.3.183	journal	April 2008
Density of Molten Salt Mixtures of Eutectic LiCl-KCl Containing UCl3, CeCl3, or LaCl3 Zhang, C.; Simpson, M. F. Journal of the Nuclear Fuel Cycle and Waste Technology(JNFCWT), Vol. 15, Issue 2 https://doi.org/10.7733/jnfcwt.2017.15.2.117	journal	June 2017

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Temperature and anion ligand field dependence of LnCl3 (Ln = Nd, Dy, Sm) electronic absorption spectra in LiCl–KCl eutectic molten salt

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Temperature and anion ligand field dependence of LnCl₃ (Ln = Nd, Dy, Sm) electronic absorption spectra in LiCl–KCl eutectic molten salt