Synthesis and Vibrational Identification of the Uranyl Peroxodicarbonato [UO2(O2)(CO3)2]4–: Insights into Peroxide-Carbonate Bonding from 18O Labeling, DFT, and QTAIM Analysis
Abstract
In carbonate-rich aqueous environments relevant to spent nuclear fuel storage, radiolytic H2O2 and carbonate species promote the formation of uranyl peroxo-carbonate complexes under mild conditions. These complexes are poorly characterized spectroscopically, with many assignments remaining controversial. This work presents the first isotope validated solution-phase identification of the peroxo-dicarbonato species Mx[UO2(O2)(CO3)2](4–x)– (M = Na+ or K+) achieved through Raman and 18O-labeled H2O2 Fourier-transform infrared (FTIR) spectroscopy, combined with density functional theory (DFT) calculations. Key vibrational signatures distinguish the peroxo-dicarbonato complex from those of the tricarbonato complex [UO2(CO3)3]4–, including the νs(U–Oyl) stretch at 765–769 cm–1, the ν(U–Operoxo) mode at 400–452 cm–1, and the ν(O–O) stretch at 845–850 cm–1, which shifts upon 18O substitution. FTIR data further confirm these assignments, providing the first infrared evidence of a uranyl peroxo-carbonato complex in aqueous solution. DFT calculations validate the observed frequencies and isotope shifts, clarifying the role of solvation and countercation effects. These results clarify uranyl peroxo-carbonato speciation, resolving long-standing ambiguities and establishing a robust spectroscopic framework for applications in uranium fuel dissolution, environmental mobility, and long-term waste stability.
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BibTeX
@article{margate2026synthesis,
title = {{Synthesis and Vibrational Identification of the Uranyl Peroxodicarbonato [UO2(O2)(CO3)2]4–: Insights into Peroxide-Carbonate Bonding from 18O Labeling, DFT, and QTAIM Analysis}},
author = {Julien Margate and Leonard Floarea and Charles Coubronne and Elise Berrier and Gaëlle Milanole and Florent Réal and Murielle Rivenet and Valérie Vallet},
journal = {Inorganic Chemistry},
year = {2026},
month = may,
doi = {10.1021/acs.inorgchem.6c00907},
url = {https://hal.science/hal-05513260v1},
note = {CC BY-NC-SA 4.0},
}
RIS
TY - JOUR
TI - Synthesis and Vibrational Identification of the Uranyl Peroxodicarbonato [UO2(O2)(CO3)2]4–: Insights into Peroxide-Carbonate Bonding from 18O Labeling, DFT, and QTAIM Analysis
AU - Julien Margate
AU - Leonard Floarea
AU - Charles Coubronne
AU - Elise Berrier
AU - Gaëlle Milanole
AU - Florent Réal
AU - Murielle Rivenet
AU - Valérie Vallet
PY - 2026
DA - 2026/05/26
JO - Inorganic Chemistry
DO - 10.1021/acs.inorgchem.6c00907
UR - https://hal.science/hal-05513260v1
AB - In carbonate-rich aqueous environments relevant to spent nuclear fuel storage, radiolytic H2O2 and carbonate species promote the formation of uranyl peroxo-carbonate complexes under mild conditions. These complexes are poorly characterized spectroscopically, with many assignments remaining controversial. This work presents the first isotope validated solution-phase identification of the peroxo-dicarbonato species Mx[UO2(O2)(CO3)2](4–x)– (M = Na+ or K+) achieved through Raman and 18O-labeled H2O2 Fourier-transform infrared (FTIR) spectroscopy, combined with density functional theory (DFT) calculations. Key vibrational signatures distinguish the peroxo-dicarbonato complex from those of the tricarbonato complex [UO2(CO3)3]4–, including the νs(U–Oyl) stretch at 765–769 cm–1, the ν(U–Operoxo) mode at 400–452 cm–1, and the ν(O–O) stretch at 845–850 cm–1, which shifts upon 18O substitution. FTIR data further confirm these assignments, providing the first infrared evidence of a uranyl peroxo-carbonato complex in aqueous solution. DFT calculations validate the observed frequencies and isotope shifts, clarifying the role of solvation and countercation effects. These results clarify uranyl peroxo-carbonato speciation, resolving long-standing ambiguities and establishing a robust spectroscopic framework for applications in uranium fuel dissolution, environmental mobility, and long-term waste stability.
SN - 0020-1669
SN - 1520-510X
ER -