title: Computationally-Guided Assignment of Unexpected Signals in the Raman Spectra of Uranyl Triperoxide Complexes.
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 by18O 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(O22-).
authors.affiliation: Department of Chemistry and Biochemistry, University of Notre Dame , Notre Dame, Indiana 46556, United States.
authors.forename: Mateusz
authors.initials: M
authors.lastname: Dembowski
authors.affiliation: Department of Chemistry, University of Minnesota, Superconducting Institute , 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
authors.forename: Varinia
authors.initials: V
authors.lastname: Bernales
authors.affiliation: Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame , Notre Dame, Indiana 46556, United States.
authors.forename: Jie
authors.initials: J
authors.lastname: Qiu
authors.affiliation: Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame , Notre Dame, Indiana 46556, United States.
authors.forename: Sarah
authors.initials: S
authors.lastname: Hickam
authors.affiliation: Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame , Notre Dame, Indiana 46556, United States.
authors.forename: Gabriel
authors.initials: G
authors.lastname: Gaspar
authors.affiliation: Department of Chemistry, University of Minnesota, Superconducting Institute , 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
authors.forename: Laura
authors.identifier: http://orcid.org/0000-0001-5227-1396
authors.initials: L
authors.lastname: Gagliardi
authors.affiliation: Department of Chemistry and Biochemistry, University of Notre Dame , Notre Dame, Indiana 46556, United States.|Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame , Notre Dame, Indiana 46556, United States.
authors.forename: Peter C
authors.identifier: http://orcid.org/0000-0002-2319-9628
authors.initials: PC
authors.lastname: Burns