基于计算指导的三过氧化铀酰配合物拉曼光谱中意外信号的归属
Computationally-Guided Assignment of Unexpected Signals in the Raman Spectra of Uranyl Triperoxide Complexes.
作者信息
Dembowski Mateusz, Bernales Varinia, Qiu Jie, Hickam Sarah, Gaspar Gabriel, Gagliardi Laura, Burns Peter C
机构信息
Department of Chemistry and Biochemistry, University of Notre Dame , Notre Dame, Indiana 46556, United States.
Department of Chemistry, University of Minnesota, Superconducting Institute , 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
出版信息
Inorg Chem. 2017 Feb 6;56(3):1574-1580. doi: 10.1021/acs.inorgchem.6b02666. Epub 2017 Jan 11.
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), (UO(O)), 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 O 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, (O).
在碱性水溶液条件下，铀、过氧化物与单价（钠、钾）或二价（镁、钙、锶）阳离子相结合，会迅速形成具有独特拉曼特征的阴离子型三过氧化铀酰单体（UTs），即（UO(O)）。电子结构计算对于光谱的解释以及与铀酰离子和过氧化物离子振动相关的意外信号的归属起着决定性作用。通过对铀酰离子进行氧同位素标记验证了这些归属，这支持了基于计算对实验观察到的峰的解释以及过氧化物配体（O）新型不对称振动的归属。
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