Quantum mechanical calculation of aqueuous uranium complexes: carbonate, phosphate, organic and biomolecular species

@article{Kubicki2009QuantumMC,
  title={Quantum mechanical calculation of aqueuous uranium complexes: carbonate, phosphate, organic and biomolecular species},
  author={James D. Kubicki and Gary Halada and Prashant K. Jha and Brian L. Phillips},
  journal={Chemistry Central Journal},
  year={2009},
  volume={3},
  pages={10 - 10}
}
BackgroundQuantum mechanical calculations were performed on a variety of uranium species representing U(VI), U(V), U(IV), U-carbonates, U-phosphates, U-oxalates, U-catecholates, U-phosphodiesters, U-phosphorylated N-acetyl-glucosamine (NAG), and U-2-Keto-3-doxyoctanoate (KDO) with explicit solvation by H2O molecules. These models represent major U species in natural waters and complexes on bacterial surfaces. The model results are compared to observed EXAFS, IR, Raman and NMR spectra… Expand
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References

SHOWING 1-10 OF 174 REFERENCES
Kinetics of triscarbonato uranyl reduction by aqueous ferrous iron: a theoretical study.
TLDR
This study examines the theoretical kinetics of ET from ferrous iron to triscarbonato uranyl in aqueous solution and concludes that U(V) is a stabilized end product in this ET system, in agreement with experiment. Expand
Complexation of the carbonate, nitrate, and acetate anions with the uranyl dication: density functional studies with relativistic effective core potentials.
TLDR
The structural and vibrational results at the LDFT level are in good agreement with experimental results and provide realistic pictures of solution phase and solid-state behavior. Expand
Role of solvation in the reduction of the uranyl dication by water: a density functional study.
TLDR
The results show that the solvation contribution to the reaction free energy, about 60 kcal/mol, dominates the endoergicity of the reduction of UO(2)(2+) by water, previously theoretically studied in the gas phase. Expand
Uranium(VI) complexes with phospholipid model compounds--a laser spectroscopic study.
TLDR
The TRLFS spectra of uranyl complexes with two phosphatidic acids, which represent the apolaric site of phospholipids, show in each case two different species, which indicates a complex formation between UO(2)(2+) and the phosphonates already at pH=2. Expand
Determination of structural parameters of uranyl ions complexed with organic acids using EXAFS
Abstract Two compounds of known crystal structure, sodium triacetatodioxouranium(VI), Na[UO 2 (CH 3 COO) 3 ], and dibenzoatodioxouranium(VI), UO 2 [C 6 H 5 (COO)] 2 , were studied by uranium L IIIExpand
X-ray absorption spectroscopy identifies calcium-uranyl-carbonate complexes at environmental concentrations☆
Current research on bioremediation of uranium-contaminated groundwater focuses on supplying indigenous metal-reducing bacteria with the appropriate metabolic requirements to induce microbiologicalExpand
Bioreduction of uranium: environmental implications of a pentavalent intermediate.
TLDR
X-ray absorption spectroscopy is used to show that the subsurface metal-reducing bacterium Geobacter sulfurreducens reduces U(VI) by a one-electron reduction, forming an unstable (UO2)+ species, illustrating the need for mechanistic understanding and care in devising in situ bioremediation strategies for complex wastes containing other redox-active actinides, including plutonium. Expand
Uranium in geologic fluids: Estimates of standard partial molal properties, oxidation potentials, and hydrolysis constants at high temperatures and pressures
Abstract Theoretical methods are used with the available experimental data to provide estimates of parameters for the revised-HKF equations of state for aqueous uranium species. These parameters areExpand
Comparative study of uranyl(VI) and -(V) carbonato complexes in an aqueous solution.
TLDR
The validity of the structural parameters obtained from EXAFS has been supported by quantum chemical calculations for the uranyl(VI) complex, and the uranium LI- and LIII-edge X-ray absorption near-edge structure spectra have been interpreted in terms of electron transitions and multiple-scattering features. Expand
Quantifying constraints imposed by calcium and iron on bacterial reduction of uranium(VI).
TLDR
The quantitative framework described herein helps to predict the fate and transport of uranium within anaerobic environments. Expand
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5
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