Rb2Ln[Si2O6]F (Ln = Y, Eu-Lu): Flux Synthesis, Structure Determination, and DFT-Calculated Formation Enthalpies of a Series of Mixed-Anion Rare Earth Cyclosilicates

Hunter B Tisdale; Amir M Mofrad; Gregory Morrison; Theodore M Besmann; Hans-Conrad Zur Loye

doi:10.1021/acs.inorgchem.3c02530

Rb₂Ln[Si₂O₆]F (Ln = Y, Eu-Lu): Flux Synthesis, Structure Determination, and DFT-Calculated Formation Enthalpies of a Series of Mixed-Anion Rare Earth Cyclosilicates

Inorg Chem. 2023 Nov 13;62(45):18440-18448. doi: 10.1021/acs.inorgchem.3c02530. Epub 2023 Oct 30.

Authors

Hunter B Tisdale^{1

2}, Amir M Mofrad^{1

3}, Gregory Morrison^{1

2}, Theodore M Besmann^{1

3}, Hans-Conrad Zur Loye^{1

2}

Affiliations

¹ Center for Hierarchical Waste form Materials, Columbia, South Carolina 29208, United States.
² Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States.
³ Department of Mechanical Engineering, University of South Carolina, Columbia, South Carolina 29208, United States.

PMID: 37903427
DOI: 10.1021/acs.inorgchem.3c02530

Abstract

A new series of mixed-anion alkali rare earth silicate fluorides with composition Rb₂Ln[Si₂O₆]F (Ln = Y, Eu-Lu) has been synthesized via an alkali chloride/fluoride eutectic flux synthetic route. All synthesized compositions crystallize in the tetragonal space group P4₂/mnm with a 3D framework consisting of LnO₄F₂ octahedra, tetrasilicate rings, and 1D channels containing alkali metals. A combination of powder X-ray diffraction, single-crystal X-ray diffraction, and luminescence emission spectroscopy was performed to characterize the reaction products. In addition, density functional theory (DFT) calculations were utilized to calculate the 0 K formation enthalpies of the synthesized phases and of hypothetical trivalent actinide analogues to probe the likelihood of the successful synthesis of such trivalent transuranic containing phases, specifically Am and Cm, in the future.