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

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

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

31 Scopus citations

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-).

Original language	English (US)
Pages (from-to)	1574-1580
Number of pages	7
Journal	Inorganic chemistry
Volume	56
Issue number	3
DOIs	https://doi.org/10.1021/acs.inorgchem.6b02666
State	Published - Feb 6 2017

Bibliographical note

Funding Information:
This work was supported by the Office of Basic Energy Sciences of the U.S. Department of Energy as part of the Materials Science of Actinides Energy Frontiers Center (DESC0001089). Raman spectroscopy measurements were conducted at the Materials Characterization Facility of the Center for Sustainable Energy at the University of Notre Dame. ICPOES measurements were conducted at the Center for Environmental Science and Technology at the University of Notre Dame.

Publisher Copyright:
© 2017 American Chemical Society.

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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 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-).",

author = "Mateusz Dembowski and Varinia Bernales and Jie Qiu and Sarah Hickam and Gabriel Gaspar and Laura Gagliardi and Burns, {Peter C.}",

note = "Funding Information: This work was supported by the Office of Basic Energy Sciences of the U.S. Department of Energy as part of the Materials Science of Actinides Energy Frontiers Center (DESC0001089). Raman spectroscopy measurements were conducted at the Materials Characterization Facility of the Center for Sustainable Energy at the University of Notre Dame. ICPOES measurements were conducted at the Center for Environmental Science and Technology at the University of Notre Dame. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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doi = "10.1021/acs.inorgchem.6b02666",

language = "English (US)",

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T1 - Computationally-Guided Assignment of Unexpected Signals in the Raman Spectra of Uranyl Triperoxide Complexes

AU - Dembowski, Mateusz

AU - Bernales, Varinia

AU - Qiu, Jie

AU - Hickam, Sarah

AU - Gaspar, Gabriel

AU - Gagliardi, Laura

AU - Burns, Peter C.

N1 - Funding Information: This work was supported by the Office of Basic Energy Sciences of the U.S. Department of Energy as part of the Materials Science of Actinides Energy Frontiers Center (DESC0001089). Raman spectroscopy measurements were conducted at the Materials Characterization Facility of the Center for Sustainable Energy at the University of Notre Dame. ICPOES measurements were conducted at the Center for Environmental Science and Technology at the University of Notre Dame. Publisher Copyright: © 2017 American Chemical Society.

PY - 2017/2/6

Y1 - 2017/2/6

N2 - 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-).

AB - 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-).

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 3

ER -

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

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