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Title: Infrared Spectroscopy of Dioxouranium (V) Complexes with Solvent Molecules: Effect of Reduction

Abstract

UO2+-solvent complexes having the general formula [UO2(ROH)]+ (R = H, CH3, C2H5, and n-C3H7) were formed using electrospray ionization and stored in a Fourier transform ion cyclotron resonance mass spectrometer, where they were isolated by mass-to-charge ratio, and then photofragmented using a free electron laser scanning through the 10 ?m region of the infrared spectrum. Antisymmetric O=U=O stretching frequencies (?3) were measured for all four complexes, which ranged from ~ 953 cm-1 for H2O to ~ 944 cm-1 for n-PrOH, with the value for the EtOH-containing complex intermediate, systematically decreasing with increasing nucleophilicity of the solvent. The value for the MeOH-containing did not follow the trend, and had a measured ?3 value equal to that of the n-PrOH-containing complex. The ?3 frequency values for these U(V) complexes are comparable to those for the anionic [UO2(NO3)3]- complex, and lower than previously reported values for ligated uranyl (VI) dication complexes by 40 – 70 cm-1, and cationic uranyl (VI) ion-pair complexes by 10 – 40 cm-1. The lower frequency is attributed to weakening of the O=U=O bonds by repulsion related to reduction of the U metal center, which increases electron density in the antibonding ?* orbitals of the uranyl moiety. Computational modellingmore » of the ?3 frequencies of these species using PBE, B3LYP and LDA functionals showed good agreement with the IRMPD measurements. In general, expected trend in ?3 frequencies expected for the H2O – MeOH – EtOH – n-PrOH series was produced by all three computational methods, however the three alcohols produced very similar values. The inverted order of MeOH and EtOH was not directly accounted for by the models, but is probably the result of overlapping C-H wagging modes that shift the apparent maxima of the O=U=O ?3 absorptions in the MeOH and EtOH complexes.« less

Authors:
; ; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Idaho National Laboratory (INL)
Sponsoring Org.:
USDOE
OSTI Identifier:
936871
Report Number(s):
INL/JOU-08-13725
Journal ID: ISSN 1439-4235; CPCHFT; TRN: US0805719
DOE Contract Number:  
DE-AC07-99ID-13727
Resource Type:
Journal Article
Journal Name:
ChemPhysChem
Additional Journal Information:
Journal Volume: 9; Journal Issue: 9; Journal ID: ISSN 1439-4235
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALCOHOLS; ELECTRON DENSITY; FREE ELECTRON LASERS; FUNCTIONALS; ION CYCLOTRON-RESONANCE; IONIZATION; MASS SPECTROMETERS; SIMULATION; SOLVENTS; SPECTROSCOPY; Infrared multiple photon dissociation spectroscop; Density Functional Theory; IRMPD; uranium; uranyl coordination complex

Citation Formats

Groenewold, Gary S, Van Stipdonk, Michael J, de Jong, Wibe A, Oomens, Jos, Gresham, Garold L, McIlwain, Michael E, Gao, Da, Siboulet, Bertrand, Visscher, Lucas, Kullman, Michael, Polfer, Nick, and Infante, Ivan. Infrared Spectroscopy of Dioxouranium (V) Complexes with Solvent Molecules: Effect of Reduction. United States: N. p., 2008. Web. doi:10.1002/cphc.200800034.
Groenewold, Gary S, Van Stipdonk, Michael J, de Jong, Wibe A, Oomens, Jos, Gresham, Garold L, McIlwain, Michael E, Gao, Da, Siboulet, Bertrand, Visscher, Lucas, Kullman, Michael, Polfer, Nick, & Infante, Ivan. Infrared Spectroscopy of Dioxouranium (V) Complexes with Solvent Molecules: Effect of Reduction. United States. https://doi.org/10.1002/cphc.200800034
Groenewold, Gary S, Van Stipdonk, Michael J, de Jong, Wibe A, Oomens, Jos, Gresham, Garold L, McIlwain, Michael E, Gao, Da, Siboulet, Bertrand, Visscher, Lucas, Kullman, Michael, Polfer, Nick, and Infante, Ivan. Sun . "Infrared Spectroscopy of Dioxouranium (V) Complexes with Solvent Molecules: Effect of Reduction". United States. https://doi.org/10.1002/cphc.200800034.
@article{osti_936871,
title = {Infrared Spectroscopy of Dioxouranium (V) Complexes with Solvent Molecules: Effect of Reduction},
author = {Groenewold, Gary S and Van Stipdonk, Michael J and de Jong, Wibe A and Oomens, Jos and Gresham, Garold L and McIlwain, Michael E and Gao, Da and Siboulet, Bertrand and Visscher, Lucas and Kullman, Michael and Polfer, Nick and Infante, Ivan},
abstractNote = {UO2+-solvent complexes having the general formula [UO2(ROH)]+ (R = H, CH3, C2H5, and n-C3H7) were formed using electrospray ionization and stored in a Fourier transform ion cyclotron resonance mass spectrometer, where they were isolated by mass-to-charge ratio, and then photofragmented using a free electron laser scanning through the 10 ?m region of the infrared spectrum. Antisymmetric O=U=O stretching frequencies (?3) were measured for all four complexes, which ranged from ~ 953 cm-1 for H2O to ~ 944 cm-1 for n-PrOH, with the value for the EtOH-containing complex intermediate, systematically decreasing with increasing nucleophilicity of the solvent. The value for the MeOH-containing did not follow the trend, and had a measured ?3 value equal to that of the n-PrOH-containing complex. The ?3 frequency values for these U(V) complexes are comparable to those for the anionic [UO2(NO3)3]- complex, and lower than previously reported values for ligated uranyl (VI) dication complexes by 40 – 70 cm-1, and cationic uranyl (VI) ion-pair complexes by 10 – 40 cm-1. The lower frequency is attributed to weakening of the O=U=O bonds by repulsion related to reduction of the U metal center, which increases electron density in the antibonding ?* orbitals of the uranyl moiety. Computational modelling of the ?3 frequencies of these species using PBE, B3LYP and LDA functionals showed good agreement with the IRMPD measurements. In general, expected trend in ?3 frequencies expected for the H2O – MeOH – EtOH – n-PrOH series was produced by all three computational methods, however the three alcohols produced very similar values. The inverted order of MeOH and EtOH was not directly accounted for by the models, but is probably the result of overlapping C-H wagging modes that shift the apparent maxima of the O=U=O ?3 absorptions in the MeOH and EtOH complexes.},
doi = {10.1002/cphc.200800034},
url = {https://www.osti.gov/biblio/936871}, journal = {ChemPhysChem},
issn = {1439-4235},
number = 9,
volume = 9,
place = {United States},
year = {2008},
month = {6}
}