Vibrational spectroscopy of anionic nitrate complexes of UO22+ and Eu3+ isolated in the gas phase

doi:https://doi.org/10.1039/b715337f

Title: Vibrational spectroscopy of anionic nitrate complexes of UO22+ and Eu3+ isolated in the gas phase

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Abstract

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

Authors:: Groenewold, G S; Gresham, G L; Van Stipdonk, M J; Oomens, J; de Jong, W A; McIlwain, M E

Publication Date:: 2008-01-01

Research Org.:: Idaho National Laboratory (INL)

Sponsoring Org.:: USDOE

OSTI Identifier:: 927437

Report Number(s):: INL/JOU-07-13265
Journal ID: ISSN 1463-9076; TRN: US0803218

DOE Contract Number:: DE-AC07-99ID-13727

Resource Type:: Journal Article

Journal Name:: Physical Chemistry Chemical Physics

Additional Journal Information:: Journal Volume: 10; Journal Issue: 8; Journal ID: ISSN 1463-9076

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTRA; DISSOCIATION; INFRARED SPECTRA; LEWIS ACIDS; NITRATES; PHOTONS; SPECTROSCOPY; density functional theory; f-element coordination complex; infrared spectroscopy

Citation Formats


                    Groenewold, G S, Gresham, G L, Van Stipdonk, M J, Oomens, J, de Jong, W A, and McIlwain, M E. Vibrational spectroscopy of anionic nitrate complexes of UO22+ and Eu3+ isolated in the gas phase.  United States: N. p., 2008. 
        Web.  doi:10.1039/b715337f.

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                    Groenewold, G S, Gresham, G L, Van Stipdonk, M J, Oomens, J, de Jong, W A, & McIlwain, M E. Vibrational spectroscopy of anionic nitrate complexes of UO22+ and Eu3+ isolated in the gas phase.  United States.  https://doi.org/10.1039/b715337f

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                    Groenewold, G S, Gresham, G L, Van Stipdonk, M J, Oomens, J, de Jong, W A, and McIlwain, M E. Tue .  
        "Vibrational spectroscopy of anionic nitrate complexes of UO22+ and Eu3+ isolated in the gas phase".  United States.  https://doi.org/10.1039/b715337f.

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@article{osti_927437,

  title        = {Vibrational spectroscopy of anionic nitrate complexes of UO22+ and Eu3+ isolated in the gas phase},

  author       = {Groenewold, G S and Gresham, G L and Van Stipdonk, M J and Oomens, J and de Jong, W A and McIlwain, M E},

  abstractNote = {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},

  doi          = {10.1039/b715337f},

  url          = {https://www.osti.gov/biblio/927437},
  journal      = {Physical Chemistry Chemical Physics},

  issn         = {1463-9076},

  number       = 8,

  volume       = 10,

  place        = {United States},

  year         = {2008},

  month        = {1}

}

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