Vibrational spectroscopy of anionic nitrate complexes of UO22+ and Eu3+ isolated in the gas phase
Wavelength-selective infrared multiple photon dissociation was used to generate infrared spectra of anionic nitrate complexes of UO22+ and Eu3+ in the mid-infrared region. A pattern of absorptions were observed for both species, including splitting of the antisymmetric O-N-O stretch into high and low frequency components with the magnitude of the splitting consistent with attachment of nitrate to a strong Lewis acid center. The frequencies measured for [UO2(NO3)3]- were within a few cm-1 of those measured in the condensed phase, the best agreement yet achieved for a comparison of IRMPD with condensed phase absorption spectra. In addition, experimentally-determined values were in good general agreement with those predicted by DFT calculations, especially for the antisymmetric UO2 stretch. The spectrum from the [UO2(NO3)3]- was compared with that of [Eu(NO3)4]-, which showed that nitrate was bound more strongly to the Eu3+ metal center, consistent with its higher charge. The spectrum of a unique uranyl-oxo species having an elemental composition [UO9N2]- was also acquired, for which calculations suggested a [UO2(NO3)2(O)]- structure
- Research Organization:
- Idaho National Laboratory (INL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC07-99ID13727
- OSTI ID:
- 927437
- Report Number(s):
- INL/JOU-07-13265
- Journal Information:
- Physical Chemistry Chemical Physics, Journal Name: Physical Chemistry Chemical Physics Journal Issue: 8 Vol. 10; ISSN 1463-9076
- Country of Publication:
- United States
- Language:
- English
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