skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: First-principles molecular dynamics simulation of the Ca2UO2(CO3)3 complex in water

Journal Article · · Dalton Transactions
DOI:https://doi.org/10.1039/c5dt04576b· OSTI ID:1435625
 [1];  [1];  [1]
  1. Univ. of California, Riverside, CA (United States)
+ Show Author Affiliations

Recent experiments have shown that the neutral Ca2UO2(CO3)3 complex is the dominant species of uranium in many uranyl-containing streams. However, the structure and solvation of such a species in water has not been investigated from first principles. Herein we present a first principles molecular dynamics perspective of the Ca2UO2(CO3)3 complex in water based on density functional theory and Born–Oppenheimer approximation. We find that the Ca2UO2(CO3)3 complex is very stable in our simulation timeframe for three different concentrations considered and that the key distances from our simulation are in good agreement with the experimental data from extended X-ray absorption fine structure (EXAFS) spectroscopy. More important, we find that the two Ca ions bind differently in the complex, as a result of the hydrogen-bonding network around the whole complex. Furthermore, this finding invites confirmation from time-resolved EXAFS and has implications in understanding the dissociative equilibrium of the Ca2UO2(CO3)3 complex in water.

Research Organization:
Univ. of California, Riverside, CA (United States)
Sponsoring Organization:
USDOE Office of Nuclear Energy (NE)
Grant/Contract Number:
NE0008397
OSTI ID:
1435625
Journal Information:
Dalton Transactions, Vol. 45, Issue 24; ISSN 1477-9226
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 23 works
Citation information provided by
Web of Science

References (40)

Investigation of ligand exchange reactions in aqueous uranyl carbonate complexes using computational approaches journal January 2011
Complexation of U(VI) with Dipicolinic Acid: Thermodynamics and Coordination Modes journal February 2013
Generalized Gradient Approximation Made Simple journal October 1996
A Comparative Quantum Mechanical Charge Field Study of Uranyl Mono- and Dicarbonate Species in Aqueous Solution journal November 2013
Tuning Amidoximate to Enhance Uranyl Binding: A Density Functional Theory Study journal October 2013
Molecular simulation of the diffusion of uranyl carbonate species in aqueous solution journal September 2010
Dispersion corrected RPBE studies of liquid water journal August 2014
Quantifying the binding strength of U( vi ) with phthalimidedioxime in comparison with glutarimidedioxime journal January 2014
Projector augmented-wave method journal December 1994
The individual and collective effects of exact exchange and dispersion interactions on the ab initio structure of liquid water journal August 2014
Interaction of uranyl ions in carbonate media journal January 1984
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Adsorption of Uranium in Sea Water Using Amidoxime Adsorbents Prepared by Radiation-Induced Cografting. [放射線共グラフト重合法により作成したアミドキシム吸着材の海域でのウラン吸着]
  • Katakai, Akio; Seko, Noriaki; Kawakami, Takashi
  • Journal of the Atomic Energy Society of Japan / Atomic Energy Society of Japan, Vol. 40, Issue 11 https://doi.org/10.3327/jaesj.40.878
journal January 1998
Chemical Speciation of Uranium(VI) in Marine Environments: Complexation of Calcium and Magnesium Ions with [(UO 2 )(CO 3 ) 3 ] 4− and the Effect on the Extraction of Uranium from Seawater journal September 2014
Structure and Dynamics of the Uranyl Tricarbonate Complex in Aqueous Solution: Insights from Quantum Mechanical Charge Field Molecular Dynamics journal September 2014
Uptake of Uranium from Seawater by Amidoxime-Based Polymeric Adsorbent: Field Experiments, Modeling, and Updated Economic Assessment journal March 2014
Energetics and Structure of Uranium(VI)–Acetate Complexes in Dimethyl Sulfoxide journal August 2012
Aquaculture of Uranium in Seawater by a Fabric-Adsorbent Submerged System journal November 2003
Uranyl(VI) carbonate complex formation: Validation of the Ca2UO2(CO3)3(aq.) species journal January 2001
Quantum mechanical calculation of aqueuous uranium complexes: carbonate, phosphate, organic and biomolecular species journal August 2009
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
X-ray absorption spectroscopy identifies calcium-uranyl-carbonate complexes at environmental concentrations journal February 2007
Complexation of calcium and magnesium with glutarimidedioxime: Implications for the extraction of uranium from seawater journal July 2015
Recovery of Uranium from Seawater: A Review of Current Status and Future Research Needs journal January 2013
Structural clues to UO 2 2+ /VO 2 + competition in seawater extraction using amidoxime-based extractants journal January 2014
Computational Study of Analogues of the Uranyl Ion Containing the −NUN− Unit:  Density Functional Theory Calculations on UO 2 2+ , UON + , UN 2 , UO(NPH 3 ) 3+ , U(NPH 3 ) 2 4+ , [UCl 4 {NPR 3 } 2 ] (R = H, Me), and [UOCl 4 {NP(C 6 H 5 ) 3 }] - journal December 2000
Formation of ternary CaUO2(CO3)32− and Ca2UO2(CO3)3(aq) complexes under neutral to weakly alkaline conditions journal January 2013
Speciation of Uranium in Seepage Waters of a Mine Tailing Pile Studied by Time-Resolved Laser-Induced Fluorescence Spectroscopy (TRLFS) journal January 1996
Preparation and performance of amidoxime fiber adsorbents for recovery of uranium from seawater journal January 1992
Alternative Alkaline Conditioning of Amidoxime Based Adsorbent for Uranium Extraction from Seawater journal October 2015
De Novo Structure-Based Design of Bis-amidoxime Uranophiles journal June 2013
Ab initiomolecular dynamics for liquid metals journal January 1993
Electronic Structure and Bonding in Actinyl Ions and their Analogs journal May 2007
Bond Evolution in Electron Transfer: A Time-Resolved EXAFS Study journal March 2010
Carbonate–H 2 O 2 leaching for sequestering uranium from seawater journal January 2014
How Amidoximate Binds the Uranyl Cation journal February 2012
VMD: Visual molecular dynamics journal February 1996
Thermodynamic studies of U(vi) complexation with glutardiamidoxime for sequestration of uranium from seawater journal January 2013
The crystal structure of Liebigite, Ca2UO2(CO3)3�?11H2O journal January 1982
Structure, Kinetics, and Thermodynamics of the Aqueous Uranyl(VI) Cation journal July 2013

Cited By (6)

X-Ray crystallographic and computational study on uranyl–salophen complexes bearing nitro groups journal January 2017
Magnetic iron oxide and manganese-doped iron oxide nanoparticles for the collection of alpha-emitting radionuclides from aqueous solutions journal January 2016
UO 2 2+ structure in solvent extraction phases resolved at molecular and supramolecular scales: a combined molecular dynamics, EXAFS and SWAXS approach journal January 2019
Formation of CaUO 2 (CO 3 ) 3 2− and Ca 2 UO 2 (CO 3 ) 3 (aq) complexes at variable temperatures (10–70 °C) journal January 2019
Complexation of UO 2 (CO 3 ) 3 4− with Mg 2+ at varying temperatures and its effect on U( vi ) speciation in groundwater and seawater journal January 2019
Spectroscopic and computational investigation of actinium coordination chemistry journal August 2016

Figures / Tables (11)

Table 1(p. 2)table Table 1
Fig. 1(p. 3)figure Fig. 1
Fig. 2(p. 3)figure Fig. 2
Fig. 3(p. 3)figure Fig. 3
Fig. 4(p. 4)figure Fig. 4
Fig. 5(p. 4)figure Fig. 5
Fig. 6(p. 5)figure Fig. 6
Fig. 7(p. 5)figure Fig. 7
Fig. 8(p. 5)figure Fig. 8
Fig. 9(p. 6)figure Fig. 9
Table 2(p. 6)table Table 2

Similar Records

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS