Theoretical study of the coordination behavior of formate and formamidoximate with dioxovanadium( v ) cation: implications for selectivity towards uranyl
Abstract
Poly(acrylamidoxime)-based fibers bearing random mixtures of carboxylate and amidoxime groups are the most widely utilized materials for extracting uranium from seawater. However, the competition between uranyl (UO22+) and vanadium ions poses a significant challenge to the industrial mining of uranium from seawater using the current generation of adsorbents. To design more selective adsorbents, a detailed understanding of how major competing ions interact with carboxylate and amidoxime ligands is required. In this work, we employ density functional theory (DFT) and wave-function methods to investigate potential binding motifs of the dioxovanadium ion, VO2+, with water, formate, and formamidoximate ligands. Employing higher level of theory calculations (CCSD(T)) resolve the existing controversy between the experimental results and previous DFT calculations for the structure of the hydrated VO2+ ion. Consistent with the EXAFS data, CCSD(T) calculations predict higher stability of the distorted octahedral geometry of VO2+(H2O)4 compared to the five-coordinate complex with a single water molecule in the second hydration shell, while all seven tested DFT methods yield the reverse stability of the two conformations. Analysis of the relative stabilities of formate-VO2+ complexes indicates that both monodentate and bidentate forms may coexist in thermodynamic equilibrium in solution, with the equilibrium balance leaning more towards themore »
- Authors:
-
- Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
- Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Nuclear Energy (NE)
- OSTI Identifier:
- 1327581
- Grant/Contract Number:
- AC05-00OR22725; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP
- Additional Journal Information:
- Journal Volume: 17; Journal Issue: 47; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
Citation Formats
Mehio, Nada, Johnson, J. Casey, Dai, Sheng, and Bryantsev, Vyacheslav S. Theoretical study of the coordination behavior of formate and formamidoximate with dioxovanadium( v ) cation: implications for selectivity towards uranyl. United States: N. p., 2015.
Web. doi:10.1039/C5CP06165B.
Mehio, Nada, Johnson, J. Casey, Dai, Sheng, & Bryantsev, Vyacheslav S. Theoretical study of the coordination behavior of formate and formamidoximate with dioxovanadium( v ) cation: implications for selectivity towards uranyl. United States. https://doi.org/10.1039/C5CP06165B
Mehio, Nada, Johnson, J. Casey, Dai, Sheng, and Bryantsev, Vyacheslav S. Wed .
"Theoretical study of the coordination behavior of formate and formamidoximate with dioxovanadium( v ) cation: implications for selectivity towards uranyl". United States. https://doi.org/10.1039/C5CP06165B. https://www.osti.gov/servlets/purl/1327581.
@article{osti_1327581,
title = {Theoretical study of the coordination behavior of formate and formamidoximate with dioxovanadium( v ) cation: implications for selectivity towards uranyl},
author = {Mehio, Nada and Johnson, J. Casey and Dai, Sheng and Bryantsev, Vyacheslav S.},
abstractNote = {Poly(acrylamidoxime)-based fibers bearing random mixtures of carboxylate and amidoxime groups are the most widely utilized materials for extracting uranium from seawater. However, the competition between uranyl (UO22+) and vanadium ions poses a significant challenge to the industrial mining of uranium from seawater using the current generation of adsorbents. To design more selective adsorbents, a detailed understanding of how major competing ions interact with carboxylate and amidoxime ligands is required. In this work, we employ density functional theory (DFT) and wave-function methods to investigate potential binding motifs of the dioxovanadium ion, VO2+, with water, formate, and formamidoximate ligands. Employing higher level of theory calculations (CCSD(T)) resolve the existing controversy between the experimental results and previous DFT calculations for the structure of the hydrated VO2+ ion. Consistent with the EXAFS data, CCSD(T) calculations predict higher stability of the distorted octahedral geometry of VO2+(H2O)4 compared to the five-coordinate complex with a single water molecule in the second hydration shell, while all seven tested DFT methods yield the reverse stability of the two conformations. Analysis of the relative stabilities of formate-VO2+ complexes indicates that both monodentate and bidentate forms may coexist in thermodynamic equilibrium in solution, with the equilibrium balance leaning more towards the formation of monodentate species. Investigations of VO2+ coordination with the formamidoximate anion has revealed the existence of seven possible binding motifs, four of which are within ~ 4.0 kcal/mol of each other. Calculations establish that the most stable binding motif entails the coordination of oxime oxygen and amide nitrogen atoms via a tautomeric rearrangement of amidoxime to imino hydroxylamine. Lastly, the difference in the most stable VO2+ and UO22+ binding conformation has important implications for the design of more selective UO22+ ligands.},
doi = {10.1039/C5CP06165B},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 47,
volume = 17,
place = {United States},
year = {Wed Oct 28 00:00:00 EDT 2015},
month = {Wed Oct 28 00:00:00 EDT 2015}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 23 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Recovery of Uranium from Seawater: A Review of Current Status and Future Research Needs
journal, January 2013
- Kim, Jungseung; Tsouris, Costas; Mayes, Richard T.
- Separation Science and Technology, Vol. 48, Issue 3
Extraction of Uranium from Sea Water
journal, September 1964
- Davies, R. V.; Kennedy, J.; McILROY, R. W.
- Nature, Vol. 203, Issue 4950
Chemical Forms of Uranium in Artificial Seawater
journal, February 1982
- Saito, Kyoichi; Miyauchi, Terukatsu
- Journal of Nuclear Science and Technology, Vol. 19, Issue 2
Soluble rare earth and actinide species in seawater
journal, December 1989
- Choppin, Gregory R.
- Marine Chemistry, Vol. 28, Issue 1-3
Development of Sorbers for the Recovery of Uranium from Seawater. 1. Assessment of Key Parameters and Screening Studies of Sorber Materials
journal, August 1982
- Schenk, H. J.; Astheimer, L.; Witte, E. G.
- Separation Science and Technology, Vol. 17, Issue 11
Development of Sorbers for the Recovery of Uranium from Seawater. Part 2. The Accumulation of Uranium from Seawater by Resins Containing Amidoxime and Imidoxime Functional Groups
journal, April 1983
- Astheimer, L.; Schenk, H. J.; Witte, E. G.
- Separation Science and Technology, Vol. 18, Issue 4
Vanadium speciation and cycling in coastal waters
journal, December 2009
- Wang, Deli; Sañudo Wilhelmy, Sergio A.
- Marine Chemistry, Vol. 117, Issue 1-4
Fractional Elution and Determination of Uranium and Vanadium Adsorbed on Amidoxime Fiber from Seawater.
journal, January 2000
- Suzuki, Toshihiro; Saito, Kyoichi; Sugo, Takanobu
- Analytical Sciences, Vol. 16, Issue 4
Determination of trace levels of dissolved vanadium in seawater by use of synthetic complexing agents and inductively coupled plasma-atomic emission spectroscopy (ICP-AES)
journal, November 2002
- Abbasse, Ghiasse; Ouddane, Baghdad; Fischer, Jean
- Analytical and Bioanalytical Chemistry, Vol. 374, Issue 5
Structural clues to UO 2 2+ /VO 2 + competition in seawater extraction using amidoxime-based extractants
journal, January 2014
- Kelley, Steven P.; Barber, Patrick S.; Mullins, Peter H. K.
- Chem. Commun., Vol. 50, Issue 83
Comparison of Amidoxime Adsorbents Prepared by Cografting Methacrylic Acid and 2-Hydroxyethyl Methacrylate with Acrylonitrile onto Polyethylene
journal, August 2000
- Kawai, Tomomi; Saito, Kyoichi; Sugita, Kazuyuki
- Industrial & Engineering Chemistry Research, Vol. 39, Issue 8
Preparation of hydrophilic amidoxime fibers by cografting acrylonitrile and methacrylic acid from an optimized monomer composition
journal, October 2000
- Kawai, Tomomi; Saito, Kyoichi; Sugita, Kazuyuki
- Radiation Physics and Chemistry, Vol. 59, Issue 4, p. 405-411
The Cambridge Structural Database: a quarter of a million crystal structures and rising
journal, May 2002
- Allen, Frank H.
- Acta Crystallographica Section B Structural Science, Vol. 58, Issue 3
Oxidative functionalisation of alkanes: synthesis, molecular structure and catalytic implications of anionic vanadium(V) oxo and peroxo complexes containing bidentate N,O ligands †
journal, January 1999
- Süss-Fink, Georg; Stanislas, Sandrine; Shul’pin, Georgiy B.
- Journal of the Chemical Society, Dalton Transactions, Issue 18
A Coordination Chemistry Study of Hydrated and Solvated Cationic Vanadium Ions in Oxidation States +III, +IV, and +V in Solution and Solid State
journal, September 2012
- Krakowiak, Joanna; Lundberg, Daniel; Persson, Ingmar
- Inorganic Chemistry, Vol. 51, Issue 18
The solvation structure and thermodynamics of aqueous vanadium cations
journal, October 2013
- Sepehr, Fatemeh; Paddison, Stephen J.
- Chemical Physics Letters, Vol. 585
Medium Effects on51V NMR Chemical Shifts: A Density Functional Study
journal, October 2001
- Bühl, Michael; Parrinello, Michele
- Chemistry - A European Journal, Vol. 7, Issue 20
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010
- Valiev, M.; Bylaska, E. J.; Govind, N.
- Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples
journal, February 1982
- Purvis, George D.; Bartlett, Rodney J.
- The Journal of Chemical Physics, Vol. 76, Issue 4
A fifth-order perturbation comparison of electron correlation theories
journal, May 1989
- Raghavachari, Krishnan; Trucks, Gary W.; Pople, John A.
- Chemical Physics Letters, Vol. 157, Issue 6
Coupled‐cluster methods with noniterative triple excitations for restricted open‐shell Hartree–Fock and other general single determinant reference functions. Energies and analytical gradients
journal, June 1993
- Watts, John D.; Gauss, Jürgen; Bartlett, Rodney J.
- The Journal of Chemical Physics, Vol. 98, Issue 11
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989
- Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 90, Issue 2
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
journal, May 1992
- Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J.
- The Journal of Chemical Physics, Vol. 96, Issue 9
MP2 energy evaluation by direct methods
journal, December 1988
- Head-Gordon, Martin; Pople, John A.; Frisch, Michael J.
- Chemical Physics Letters, Vol. 153, Issue 6
Note on an Approximation Treatment for Many-Electron Systems
journal, October 1934
- Møller, Chr.; Plesset, M. S.
- Physical Review, Vol. 46, Issue 7
Inhomogeneous Electron Gas
journal, November 1964
- Hohenberg, P.; Kohn, W.
- Physical Review, Vol. 136, Issue 3B, p. B864-B871
Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965
- Kohn, W.; Sham, L. J.
- Physical Review, Vol. 140, Issue 4A, p. A1133-A1138
Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg
journal, January 1985
- Hay, P. Jeffrey; Wadt, Willard R.
- The Journal of Chemical Physics, Vol. 82, Issue 1
Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals
journal, January 1985
- Hay, P. Jeffrey; Wadt, Willard R.
- The Journal of Chemical Physics, Vol. 82, Issue 1, p. 299-310
Ab initio effective core potentials for molecular calculations. Potentials for main group elements Na to Bi
journal, January 1985
- Wadt, Willard R.; Hay, P. Jeffrey
- The Journal of Chemical Physics, Vol. 82, Issue 1
Revised Basis Sets for the LANL Effective Core Potentials
journal, June 2008
- Roy, Lindsay E.; Hay, P. Jeffrey; Martin, Richard L.
- Journal of Chemical Theory and Computation, Vol. 4, Issue 7
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)]
journal, February 1997
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 78, Issue 7
Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993
- Becke, Axel D.
- The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988
- Lee, Chengteh; Yang, Weitao; Parr, Robert G.
- Physical Review B, Vol. 37, Issue 2
Systematic optimization of long-range corrected hybrid density functionals
journal, February 2008
- Chai, Jeng-Da; Head-Gordon, Martin
- The Journal of Chemical Physics, Vol. 128, Issue 8
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections
journal, January 2008
- Chai, Jeng-Da; Head-Gordon, Martin
- Physical Chemistry Chemical Physics, Vol. 10, Issue 44
Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006
- Grimme, Stefan
- Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
Effect of the damping function in dispersion corrected density functional theory
journal, March 2011
- Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars
- Journal of Computational Chemistry, Vol. 32, Issue 7
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals
journal, July 2007
- Zhao, Yan; Truhlar, Donald G.
- Theoretical Chemistry Accounts, Vol. 120, Issue 1-3
Climbing the Density Functional Ladder: Nonempirical Meta–Generalized Gradient Approximation Designed for Molecules and Solids
journal, September 2003
- Tao, Jianmin; Perdew, John P.; Staroverov, Viktor N.
- Physical Review Letters, Vol. 91, Issue 14
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010
- Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
- The Journal of Chemical Physics, Vol. 132, Issue 15
A new integral equation formalism for the polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics
journal, August 1997
- Cancès, E.; Mennucci, B.; Tomasi, J.
- The Journal of Chemical Physics, Vol. 107, Issue 8
Evaluation of Solvent Effects in Isotropic and Anisotropic Dielectrics and in Ionic Solutions with a Unified Integral Equation Method: Theoretical Bases, Computational Implementation, and Numerical Applications
journal, December 1997
- Mennucci, B.; Cancès, E.; Tomasi, J.
- The Journal of Physical Chemistry B, Vol. 101, Issue 49
Uranyl-Glycine-Water Complexes in Solution: Comprehensive Computational Modeling of Coordination Geometries, Stabilization Energies, and Luminescence Properties
journal, March 2011
- Su, Jing; Zhang, Kai; Schwarz, W. H. Eugen
- Inorganic Chemistry, Vol. 50, Issue 6
How Amidoximate Binds the Uranyl Cation
journal, February 2012
- Vukovic, Sinisa; Watson, Lori A.; Kang, Sung Ok
- Inorganic Chemistry, Vol. 51, Issue 6
Theoretical investigation of tautomerism in N-hydroxy amidines
journal, January 2009
- Tavakol, Hossein; Arshadi, Sattar
- Journal of Molecular Modeling, Vol. 15, Issue 7
Crystal structures of bis[2,2'-iminobis(acetamidoxime)]nickel(II) chloride dihydrate and bis[2,2'-iminobis(acetamidoxime)]copper(II) chloride
journal, August 1970
- Cullen, David L.; Lingafelter, Edward C.
- Inorganic Chemistry, Vol. 9, Issue 8
Crystal structure of bis(acetato-κ O )bis(pyridine-2-carboxamide oxime-κ 2 N , N ′)cadmium ethanol disolvate
journal, August 2014
- Liu, Jiyong
- Acta Crystallographica Section E Structure Reports Online, Vol. 70, Issue 9
Metal complexes of purine-N-oxides. I. The crystal structure of a copper(II) complex of doubly deprotonated adenine-N1-oxide
journal, September 1984
- Sletten, Einar; Marthinsen, Terje; Sletten, Jorunn
- Inorganica Chimica Acta, Vol. 93, Issue 1
Structure–activity relationship disturbed by a solvolytic process: Study on the [Cu(II)-4-nitropyridine N-oxide derivative] system
journal, February 2013
- Puszko, Aniela; Kochel, Andrzej; Wietrzyk, Joanna
- Polyhedron, Vol. 50, Issue 1
Coordination chemistry of polyoxomolybdates: The versatile behavior of amidoximes
journal, December 1996
- Roh, Soo-Gyun; Proust, Anna; Robert, Francis
- Journal of Cluster Science, Vol. 7, Issue 4
Predicting Stability Constants for Uranyl Complexes Using Density Functional Theory
journal, March 2015
- Vukovic, Sinisa; Hay, Benjamin P.; Bryantsev, Vyacheslav S.
- Inorganic Chemistry, Vol. 54, Issue 8
Works referencing / citing this record:
Origin of the unusually strong and selective binding of vanadium by polyamidoximes in seawater
journal, November 2017
- Ivanov, Alexander S.; Leggett, Christina J.; Parker, Bernard F.
- Nature Communications, Vol. 8, Issue 1
Structural and computational characterization of a bridging zwitterionic-amidoxime uranyl complex
journal, January 2019
- Decato, Daniel A.; Berryman, Orion B.
- Organic Chemistry Frontiers, Vol. 6, Issue 7
Lanthanide complexes with zwitterionic amidoximes stabilized by noncoordinating water molecules
journal, November 2017
- Kelley, Steven P.; Rogers, Robin D.
- Supramolecular Chemistry, Vol. 30, Issue 5-6