Pronounced Pressure Dependence of Electronic Transitions for Americium Compared to Isomorphous Neodymium and Samarium Mellitates

The mellitate ion is relevant in spent nuclear fuel processing and is utilized as a surrogate for studying the interactions of f elements with humic acids. A wealth of different coordination modes gives the potential for diverse structural chemistry across the actinide series. In this study, an amer...

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Published in:Inorganic chemistry 2021-01, Vol.60 (1), p.476-483
Main Authors: Sperling, Joseph M, Warzecha, Evan, Klamm, Bonnie E, Gaiser, Alyssa N, Windorff, Cory J, Whitefoot, Megan A, Albrecht-Schönzart, Thomas E
Format: Article
Language:English
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Summary:The mellitate ion is relevant in spent nuclear fuel processing and is utilized as a surrogate for studying the interactions of f elements with humic acids. A wealth of different coordination modes gives the potential for diverse structural chemistry across the actinide series. In this study, an americium mellitate, Am [(C (COO ) ](H O) ·2H O ( ), has been synthesized and characterized using structural analysis and spectroscopy at ambient and elevated pressures. was then compared to isomorphous neodymium ( ) and samarium ( ) mellitates via bond-length analysis and pressure dependence of their Laporte-forbidden f → f transitions. Results show that the pressure dependence of the f → f transitions of is significantly greater than that observed in and , with average shifts of 21.4, 4.7, and 3.6 cm /GPa, respectively. This greater shift found in shows further evidence that the 5f orbitals are more affected than the 4f orbitals when pressure is applied to isostructural compounds.
ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.0c03293