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

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:
; ; ; ; ;
Publication Date:
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.
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
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.
@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}
}