Computationally-Guided Assignment of Unexpected Signals in the Raman Spectra of Uranyl Triperoxide Complexes

Mateusz Dembowski; Varinia Bernales; Jie Qiu; Sarah Hickam; Gabriel Gaspar; Laura Gagliardi; Peter C Burns

doi:10.1021/acs.inorgchem.6b02666

Computationally-Guided Assignment of Unexpected Signals in the Raman Spectra of Uranyl Triperoxide Complexes

Inorg Chem. 2017 Feb 6;56(3):1574-1580. doi: 10.1021/acs.inorgchem.6b02666. Epub 2017 Jan 11.

Authors

Mateusz Dembowski¹, Varinia Bernales², Jie Qiu³, Sarah Hickam³, Gabriel Gaspar³, Laura Gagliardi², Peter C Burns^{1

3}

Affiliations

¹ Department of Chemistry and Biochemistry, University of Notre Dame , Notre Dame, Indiana 46556, United States.
² Department of Chemistry, University of Minnesota, Superconducting Institute , 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
³ Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame , Notre Dame, Indiana 46556, United States.

PMID: 28075121
DOI: 10.1021/acs.inorgchem.6b02666

Abstract

Combination of uranium, peroxide, and mono- (Na, K) or divalent (Mg, Ca, Sr) cations under alkaline aqueous conditions results in the rapid formation of anionic uranyl triperoxide monomers (UTs), (UO₂(O₂)₃)^4-, exhibiting unique Raman signatures. Electronic structure calculations were decisive for the interpretation of the spectra and assignment of unexpected signals associated with vibrations of the uranyl and peroxide ions. Assignments were verified by ¹⁸O isotopic labeling of the uranyl ions supporting the computational-based interpretation of the experimentally observed peaks and the assignment of a novel asymmetric vibration of the peroxide ligands, _v2(O₂^2-).