1. Measurement of the asymmetric UO22+ stretching frequency for [UVIO2(F)3]- using IRMPD spectroscopy
- Author
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Jonathan Martens, Jos Oomens, Theodore A. Corcovilos, Giel Berden, Amanda R. Bubas, Irena Tatosian, Michael J. Van Stipdonk, Connor Graca, Luke J. Metzler, and Molecular Spectroscopy (HIMS, FNWI)
- Subjects
FELIX Molecular Structure and Dynamics ,Infrared ,Chemistry ,010401 analytical chemistry ,Photodissociation ,Analytical chemistry ,010402 general chemistry ,Condensed Matter Physics ,Uranyl ,01 natural sciences ,0104 chemical sciences ,chemistry.chemical_compound ,Density functional theory ,Infrared multiphoton dissociation ,Physical and Theoretical Chemistry ,Spectroscopy ,Instrumentation - Abstract
In a previous study [Int. J. Mass Spectrom. 2010; 297: 67–75], the asymmetric O=U=O stretch (ν3) was measured for anionic uranyl complexes with composition [UO2(X)3]-, X = Cl-, Br- and I-. Within this group of complexes, the ν3 frequency red-shifts following the trend I > Br > Cl, suggesting concomitant weakening of the U=O bonds. However, a value for [UO2(F)3]- was not measured, which prevented a comprehensive comparison of measured ν3 positions to computed frequencies from density functional theory (DFT) calculations. Because the shift in ν3 is predicted to be most dramatic when X = F, we revisited these species using infrared multiple-photon photodissociation spectroscopy. As in our earlier study, a modest red-shift to the ν3 vibration of ∼ 6 cm-1 was observed for X = I-, Br-, and Cl-, and the position of the frequency follows the trend I- > Br- > Cl-. The value measured for [UO2(F)3]- is ∼43 cm-1 lower than the one measured for [UO2(Cl)3]-. Overall, the trend with respect to ν3 position is reproduced well by computed frequencies from DFT.
- Published
- 2019
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