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Title: Ion association with tetra- n-alkylammonium cations stabilizes higher-oxidation-state neptunium dioxocations

Abstract

Extended–coordination sphere interactions between dissolved metals and other ions, including electrolyte cations, are not known to perturb the electrochemical behavior of metal cations in water. Herein, we report the stabilization of higher–oxidation state Np dioxocations in aqueous chloride solutions by hydrophobic tetra-nalkylammonium (TAA +) cations—an effect not exerted by fully hydrated Li + cations under similar conditions. Experimental and molecular dynamics simulation results indicate that TAA + cations not only drive enhanced coordination of anionic Cl ligands to Np V/VI but also associate with the resulting Np complexes via non-covalent interactions, which together decrease the electrode potential of the Np VI/Np V couple by up to 220 mV (ΔΔG = –22.2 kJ mol –1). Understanding the solvation–dependent interplay between electrolyte cations and metal–oxo species opens an avenue for controlling the formation and redox properties of metal complexes in solution. As a result, it also provides valuable mechanistic insights into actinide separation processes that widely use quaternary ammonium cations as extractants or in room temperature ionic liquids.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]
  1. Argonne National Lab. (ANL), Argonne, IL (United States); Clemson Univ., Anderson, SC (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States); 3M Corporate Research Analytical Lab., St. Paul, MN (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1494551
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Estes, Shanna L., Qiao, Baofu, and Jin, Geng Bang. Ion association with tetra-n-alkylammonium cations stabilizes higher-oxidation-state neptunium dioxocations. United States: N. p., 2019. Web. doi:10.1038/s41467-018-07982-5.
Estes, Shanna L., Qiao, Baofu, & Jin, Geng Bang. Ion association with tetra-n-alkylammonium cations stabilizes higher-oxidation-state neptunium dioxocations. United States. doi:10.1038/s41467-018-07982-5.
Estes, Shanna L., Qiao, Baofu, and Jin, Geng Bang. Fri . "Ion association with tetra-n-alkylammonium cations stabilizes higher-oxidation-state neptunium dioxocations". United States. doi:10.1038/s41467-018-07982-5. https://www.osti.gov/servlets/purl/1494551.
@article{osti_1494551,
title = {Ion association with tetra-n-alkylammonium cations stabilizes higher-oxidation-state neptunium dioxocations},
author = {Estes, Shanna L. and Qiao, Baofu and Jin, Geng Bang},
abstractNote = {Extended–coordination sphere interactions between dissolved metals and other ions, including electrolyte cations, are not known to perturb the electrochemical behavior of metal cations in water. Herein, we report the stabilization of higher–oxidation state Np dioxocations in aqueous chloride solutions by hydrophobic tetra-nalkylammonium (TAA+) cations—an effect not exerted by fully hydrated Li+ cations under similar conditions. Experimental and molecular dynamics simulation results indicate that TAA+ cations not only drive enhanced coordination of anionic Cl– ligands to NpV/VI but also associate with the resulting Np complexes via non-covalent interactions, which together decrease the electrode potential of the NpVI/NpV couple by up to 220 mV (ΔΔG = –22.2 kJ mol–1). Understanding the solvation–dependent interplay between electrolyte cations and metal–oxo species opens an avenue for controlling the formation and redox properties of metal complexes in solution. As a result, it also provides valuable mechanistic insights into actinide separation processes that widely use quaternary ammonium cations as extractants or in room temperature ionic liquids.},
doi = {10.1038/s41467-018-07982-5},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {1}
}

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Cited by: 3 works
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Figures / Tables:

Fig. 1 Fig. 1: Effect of Li+ vs. [NMe4]+ on the NpVI/NpV couple. Currentnormalized cyclic voltammetry data for solutions of 5 mM NpV dissolved in 5M NMe4Cl or 5 M LiCl at pH ≈ 1.3. The arrow indicates the initial scan direction. Initial and cathodic switching potential= 400/550mV; anodic switching potential= 1000/1150mV;more » ν= 100mV s−1« less

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Works referenced in this record:

The electrochemical behavior of cerium(III/IV) complexes: Thermodynamics, kinetics and applications in synthesis
journal, February 2014

  • Piro, Nicholas A.; Robinson, Jerome R.; Walsh, Patrick J.
  • Coordination Chemistry Reviews, Vol. 260
  • DOI: 10.1016/j.ccr.2013.08.034

Development and application of effective pairwise potentials for UO2n+, NpO2n+, PuO2n+, and AmO2n+ (n = 1, 2) ions with water
journal, January 2013

  • Pomogaev, Vladimir; Tiwari, Surya Prakash; Rai, Neeraj
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 38
  • DOI: 10.1039/c3cp52444b

Intensities in the Spectra of Actinyl Ions
journal, December 2000

  • Matsika, Spiridoula; Pitzer, Russell M.; Reed, Donald T.
  • The Journal of Physical Chemistry A, Vol. 104, Issue 51
  • DOI: 10.1021/jp002580s

The Raman Scattering of Uranyl and Transuranium V, VI, and VII Ions
journal, March 1974


The Determination of Consecutive Formation Constants of Complex Ions from Polarographic Data
journal, November 1951

  • DeFord, Donald D.; Hume, David N.
  • Journal of the American Chemical Society, Vol. 73, Issue 11
  • DOI: 10.1021/ja01155a093

A short history of SHELX
journal, December 2007

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
  • DOI: 10.1107/S0108767307043930

Theoretical and experimental study of the vibrational frequencies of UO2 2+ and NpO2 2+ in highly concentrated chloride solutions
journal, July 2014

  • Fujii, Toshiyuki; Uehara, Akihiro; Kitatsuji, Yoshihiro
  • Journal of Radioanalytical and Nuclear Chemistry, Vol. 303, Issue 1
  • DOI: 10.1007/s10967-014-3340-6

A Comparison of Neptunyl(V) and Neptunyl(VI) Solution Coordination: The Stability of Cation−Cation Interactions
journal, June 2008

  • Skanthakumar, S.; Antonio, Mark R.; Soderholm, L.
  • Inorganic Chemistry, Vol. 47, Issue 11
  • DOI: 10.1021/ic702478w

The Mechanism of Water Exchange in AmO 2 (H 2 O) 5 2+ and in the Isoelectronic UO 2 (H 2 O) 5 + and NpO 2 (H 2 O) 5 2+ Complexes as Studied by Quantum Chemical Methods
journal, June 2004

  • Vallet, Valérie; Privalov, Timofei; Wahlgren, Ulf
  • Journal of the American Chemical Society, Vol. 126, Issue 25
  • DOI: 10.1021/ja0483544

Lanthanides and Actinides in Ionic Liquids
journal, June 2007


GROMACS 4:  Algorithms for Highly Efficient, Load-Balanced, and Scalable Molecular Simulation
journal, February 2008

  • Hess, Berk; Kutzner, Carsten; van der Spoel, David
  • Journal of Chemical Theory and Computation, Vol. 4, Issue 3
  • DOI: 10.1021/ct700301q

Redox-inactive metals modulate the reduction potential in heterometallic manganese–oxido clusters
journal, March 2013

  • Tsui, Emily Y.; Tran, Rosalie; Yano, Junko
  • Nature Chemistry, Vol. 5, Issue 4
  • DOI: 10.1038/nchem.1578

Influence of Countercation Hydration Enthalpies on the Formation of Molecular Complexes: A Thorium–Nitrate Example
journal, November 2017

  • Jin, Geng Bang; Lin, Jian; Estes, Shanna L.
  • Journal of the American Chemical Society, Vol. 139, Issue 49
  • DOI: 10.1021/jacs.7b09363

Cation–cation interactions between NpO2+ and UO22+ at different temperatures and ionic strengths
journal, January 2012

  • Xian, Liang; Tian, Guoxin; Zheng, Weifang
  • Dalton Transactions, Vol. 41, Issue 28
  • DOI: 10.1039/c2dt30736g

Specific Interaction between Np(V) and U(VI) in Aqueous Perchloric Acid Media 1
journal, August 1961

  • Sullivan, J. C.; Hindman, J. C.; Zielen, A. J.
  • Journal of the American Chemical Society, Vol. 83, Issue 16
  • DOI: 10.1021/ja01477a004

Probing the Nature of Chemical Bonding in Uranyl(VI) Complexes with Quantum Chemical Methods
journal, November 2012

  • Vallet, Valérie; Wahlgren, Ulf; Grenthe, Ingmar
  • The Journal of Physical Chemistry A, Vol. 116, Issue 50
  • DOI: 10.1021/jp3091123

Uranyl to Uranium(IV) Conversion through Manipulation of Axial and Equatorial Ligands
journal, February 2018

  • Bell, Nicola L.; Shaw, Brian; Arnold, Polly L.
  • Journal of the American Chemical Society, Vol. 140, Issue 9
  • DOI: 10.1021/jacs.7b13474

Raman spectrometric studies of "cation-cation" complexes of pentavalent actinides in aqueous perchlorate solutions
journal, March 1982

  • Guillaume, B.; Begun, G. M.; Hahn, R. L.
  • Inorganic Chemistry, Vol. 21, Issue 3
  • DOI: 10.1021/ic00133a055

Uranium and manganese assembled in a wheel-shaped nanoscale single-molecule magnet with high spin-reversal barrier
journal, November 2012

  • Mougel, Victor; Chatelain, Lucile; Pécaut, Jacques
  • Nature Chemistry, Vol. 4, Issue 12
  • DOI: 10.1038/nchem.1494

Ion Pairing
journal, November 2006

  • Marcus, Yizhak; Hefter, Glenn
  • Chemical Reviews, Vol. 106, Issue 11
  • DOI: 10.1021/cr040087x

Electron-Transfer Kinetics of Np[sup 3+]∕Np[sup 4+], NpO[sub 2][sup +]∕NpO[sub 2][sup 2+], V[sup 2+]∕V[sup 3+], and VO[sup 2+]∕VO[sub 2][sup +] at Carbon Electrodes
journal, January 2005

  • Yamamura, Tomoo; Watanabe, Nobutaka; Yano, Takashi
  • Journal of The Electrochemical Society, Vol. 152, Issue 4
  • DOI: 10.1149/1.1870794

Aqueous uranium complexes. 2. Raman spectroscopic study of the complex formation of the dioxouranium(VI) ion with a variety of inorganic and organic ligands
journal, December 1992

  • Nguyen Trung, Chinh; Begun, G. M.; Palmer, Donald A.
  • Inorganic Chemistry, Vol. 31, Issue 25
  • DOI: 10.1021/ic00051a021

Cation−Cation Interactions between Uranyl Cations in a Polar Open-Framework Uranyl Periodate
journal, March 2004

  • Sullens, Tyler A.; Jensen, Rebecca A.; Shvareva, Tatiana Y.
  • Journal of the American Chemical Society, Vol. 126, Issue 9
  • DOI: 10.1021/ja031695h

Neptunium Carbonato Complexes in Aqueous Solution: An Electrochemical, Spectroscopic, and Quantum Chemical Study
journal, December 2009

  • Ikeda-Ohno, Atsushi; Tsushima, Satoru; Takao, Koichiro
  • Inorganic Chemistry, Vol. 48, Issue 24
  • DOI: 10.1021/ic901838r

Three New Sodium Neptunyl(V) Selenate Hydrates: Structures, Raman Spectroscopy, and Magnetism
journal, February 2012

  • Jin, Geng Bang; Skanthakumar, S.; Soderholm, L.
  • Inorganic Chemistry, Vol. 51, Issue 5
  • DOI: 10.1021/ic202703j

Pentavalent Neptunyl ([O≡Np≡O]+) Cation–Cation Interactions in Aqueous/Polar Organic Mixed-Solvent Media
journal, June 2017

  • Burn, Adam G.; Martin, Leigh R.; Nash, Kenneth L.
  • Journal of Solution Chemistry, Vol. 46, Issue 6
  • DOI: 10.1007/s10953-017-0647-2

Synthesis and single crystal X-ray diffraction study of U(VI), Np(VI), and Pu(VI) perchlorate hydrates
journal, August 2010


Reduction and selective oxo group silylation of the uranyl dication
journal, January 2008

  • Arnold, Polly L.; Patel, Dipti; Wilson, Claire
  • Nature, Vol. 451, Issue 7176
  • DOI: 10.1038/nature06467

A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO 2 ·M] 4+ Cation–Cation Complexes
journal, April 2017


Crystal structure of a metal ion-bound oxoiron(IV) complex and implications for biological electron transfer
journal, July 2010

  • Fukuzumi, Shunichi; Morimoto, Yuma; Kotani, Hiroaki
  • Nature Chemistry, Vol. 2, Issue 9
  • DOI: 10.1038/nchem.731

Mixed-Valent Neptunium(IV/V) Compound with Cation–Cation-Bound Six-Membered Neptunyl Rings
journal, October 2013


Spectrophotometry of Neptunium in Perchloric Acid Solutions 1
journal, April 1951

  • Sjoblom, R.; Hindman, J. C.
  • Journal of the American Chemical Society, Vol. 73, Issue 4
  • DOI: 10.1021/ja01148a091

Control of cerium oxidation state through metal complex secondary structures
journal, January 2015

  • Levin, Jessica R.; Dorfner, Walter L.; Carroll, Patrick J.
  • Chemical Science, Vol. 6, Issue 12
  • DOI: 10.1039/C5SC02607E

Redox Energetics and Kinetics of Uranyl Coordination Complexes in Aqueous Solution
journal, July 2002


Energetics and hydration of the constituent ion pairs of tetramethylammonium chloride
journal, March 1989

  • Buckner, J. Kathleen; Jorgensen, William L.
  • Journal of the American Chemical Society, Vol. 111, Issue 7
  • DOI: 10.1021/ja00189a023

XANES Spectroelectrochemistry:  A New Method for Determining Formal Potentials
journal, October 1999

  • Soderholm, L.; Antonio, Mark R.; Williams, Clayton
  • Analytical Chemistry, Vol. 71, Issue 20
  • DOI: 10.1021/ac990080t

Electronic Structure and Bonding in Actinyl Ions and their Analogs
journal, May 2007

  • Denning, Robert G.
  • The Journal of Physical Chemistry A, Vol. 111, Issue 20
  • DOI: 10.1021/jp071061n

Exploring the Effects of Reduction or Lewis Acid Coordination on the UO Bond of the Uranyl Moiety
journal, April 2009

  • Hayton, Trevor W.; Wu, Guang
  • Inorganic Chemistry, Vol. 48, Issue 7
  • DOI: 10.1021/ic802360y

Solvation of Uranyl(II), Europium(III) and Europium(II) Cations in“Basic” Room-Temperature Ionic Liquids: A Theoretical Study
journal, August 2004

  • Chaumont, Alain; Wipff, Georges
  • Chemistry - A European Journal, Vol. 10, Issue 16
  • DOI: 10.1002/chem.200400207

Role of the Uranyl Oxo Group as a Hydrogen Bond Acceptor
journal, March 2011

  • Watson, Lori A.; Hay, Benjamin P.
  • Inorganic Chemistry, Vol. 50, Issue 6
  • DOI: 10.1021/ic102448q

The Sulfate Coordination of Np(IV), Np(V), and Np(VI) in Aqueous Solution
journal, June 2009

  • Hennig, Christoph; Ikeda-Ohno, Atsushi; Tsushima, Satoru
  • Inorganic Chemistry, Vol. 48, Issue 12
  • DOI: 10.1021/ic9003005

Investigation of Aquo and Chloro Complexes of UO 2 2+ , NpO 2 + , Np 4+ , and Pu 3+ by X-ray Absorption Fine Structure Spectroscopy
journal, October 1997

  • Allen, P. G.; Bucher, J. J.; Shuh, D. K.
  • Inorganic Chemistry, Vol. 36, Issue 21
  • DOI: 10.1021/ic970502m

    Works referencing / citing this record:

    Solvation of Uranyl(II), Europium(III) and Europium(II) Cations in“Basic” Room-Temperature Ionic Liquids: A Theoretical Study
    journal, August 2004

    • Chaumont, Alain; Wipff, Georges
    • Chemistry - A European Journal, Vol. 10, Issue 16
    • DOI: 10.1002/chem.200400207

    Pentavalent Neptunyl ([O≡Np≡O]+) Cation–Cation Interactions in Aqueous/Polar Organic Mixed-Solvent Media
    journal, June 2017

    • Burn, Adam G.; Martin, Leigh R.; Nash, Kenneth L.
    • Journal of Solution Chemistry, Vol. 46, Issue 6
    • DOI: 10.1007/s10953-017-0647-2

    Theoretical and experimental study of the vibrational frequencies of UO2 2+ and NpO2 2+ in highly concentrated chloride solutions
    journal, July 2014

    • Fujii, Toshiyuki; Uehara, Akihiro; Kitatsuji, Yoshihiro
    • Journal of Radioanalytical and Nuclear Chemistry, Vol. 303, Issue 1
    • DOI: 10.1007/s10967-014-3340-6

    The electrochemical behavior of cerium(III/IV) complexes: Thermodynamics, kinetics and applications in synthesis
    journal, February 2014

    • Piro, Nicholas A.; Robinson, Jerome R.; Walsh, Patrick J.
    • Coordination Chemistry Reviews, Vol. 260
    • DOI: 10.1016/j.ccr.2013.08.034

    XANES Spectroelectrochemistry:  A New Method for Determining Formal Potentials
    journal, October 1999

    • Soderholm, L.; Antonio, Mark R.; Williams, Clayton
    • Analytical Chemistry, Vol. 71, Issue 20
    • DOI: 10.1021/ac990080t

    A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO 2 ·M] 4+ Cation–Cation Complexes
    journal, April 2017


    Ion Pairing
    journal, November 2006

    • Marcus, Yizhak; Hefter, Glenn
    • Chemical Reviews, Vol. 106, Issue 11
    • DOI: 10.1021/cr040087x

    Lanthanides and Actinides in Ionic Liquids
    journal, June 2007


    GROMACS 4:  Algorithms for Highly Efficient, Load-Balanced, and Scalable Molecular Simulation
    journal, February 2008

    • Hess, Berk; Kutzner, Carsten; van der Spoel, David
    • Journal of Chemical Theory and Computation, Vol. 4, Issue 3
    • DOI: 10.1021/ct700301q

    Aqueous uranium complexes. 2. Raman spectroscopic study of the complex formation of the dioxouranium(VI) ion with a variety of inorganic and organic ligands
    journal, December 1992

    • Nguyen Trung, Chinh; Begun, G. M.; Palmer, Donald A.
    • Inorganic Chemistry, Vol. 31, Issue 25
    • DOI: 10.1021/ic00051a021

    Raman spectrometric studies of "cation-cation" complexes of pentavalent actinides in aqueous perchlorate solutions
    journal, March 1982

    • Guillaume, B.; Begun, G. M.; Hahn, R. L.
    • Inorganic Chemistry, Vol. 21, Issue 3
    • DOI: 10.1021/ic00133a055

    Redox Energetics and Kinetics of Uranyl Coordination Complexes in Aqueous Solution
    journal, July 2002


    Role of the Uranyl Oxo Group as a Hydrogen Bond Acceptor
    journal, March 2011

    • Watson, Lori A.; Hay, Benjamin P.
    • Inorganic Chemistry, Vol. 50, Issue 6
    • DOI: 10.1021/ic102448q

    Three New Sodium Neptunyl(V) Selenate Hydrates: Structures, Raman Spectroscopy, and Magnetism
    journal, February 2012

    • Jin, Geng Bang; Skanthakumar, S.; Soderholm, L.
    • Inorganic Chemistry, Vol. 51, Issue 5
    • DOI: 10.1021/ic202703j

    Mixed-Valent Neptunium(IV/V) Compound with Cation–Cation-Bound Six-Membered Neptunyl Rings
    journal, October 2013


    A Comparison of Neptunyl(V) and Neptunyl(VI) Solution Coordination: The Stability of Cation−Cation Interactions
    journal, June 2008

    • Skanthakumar, S.; Antonio, Mark R.; Soderholm, L.
    • Inorganic Chemistry, Vol. 47, Issue 11
    • DOI: 10.1021/ic702478w

    Exploring the Effects of Reduction or Lewis Acid Coordination on the UO Bond of the Uranyl Moiety
    journal, April 2009

    • Hayton, Trevor W.; Wu, Guang
    • Inorganic Chemistry, Vol. 48, Issue 7
    • DOI: 10.1021/ic802360y

    The Sulfate Coordination of Np(IV), Np(V), and Np(VI) in Aqueous Solution
    journal, June 2009

    • Hennig, Christoph; Ikeda-Ohno, Atsushi; Tsushima, Satoru
    • Inorganic Chemistry, Vol. 48, Issue 12
    • DOI: 10.1021/ic9003005

    Neptunium Carbonato Complexes in Aqueous Solution: An Electrochemical, Spectroscopic, and Quantum Chemical Study
    journal, December 2009

    • Ikeda-Ohno, Atsushi; Tsushima, Satoru; Takao, Koichiro
    • Inorganic Chemistry, Vol. 48, Issue 24
    • DOI: 10.1021/ic901838r

    Investigation of Aquo and Chloro Complexes of UO 2 2+ , NpO 2 + , Np 4+ , and Pu 3+ by X-ray Absorption Fine Structure Spectroscopy
    journal, October 1997

    • Allen, P. G.; Bucher, J. J.; Shuh, D. K.
    • Inorganic Chemistry, Vol. 36, Issue 21
    • DOI: 10.1021/ic970502m

    Energetics and hydration of the constituent ion pairs of tetramethylammonium chloride
    journal, March 1989

    • Buckner, J. Kathleen; Jorgensen, William L.
    • Journal of the American Chemical Society, Vol. 111, Issue 7
    • DOI: 10.1021/ja00189a023

    Spectrophotometry of Neptunium in Perchloric Acid Solutions 1
    journal, April 1951

    • Sjoblom, R.; Hindman, J. C.
    • Journal of the American Chemical Society, Vol. 73, Issue 4
    • DOI: 10.1021/ja01148a091

    The Determination of Consecutive Formation Constants of Complex Ions from Polarographic Data
    journal, November 1951

    • DeFord, Donald D.; Hume, David N.
    • Journal of the American Chemical Society, Vol. 73, Issue 11
    • DOI: 10.1021/ja01155a093

    Specific Interaction between Np(V) and U(VI) in Aqueous Perchloric Acid Media 1
    journal, August 1961

    • Sullivan, J. C.; Hindman, J. C.; Zielen, A. J.
    • Journal of the American Chemical Society, Vol. 83, Issue 16
    • DOI: 10.1021/ja01477a004

    Cation−Cation Interactions between Uranyl Cations in a Polar Open-Framework Uranyl Periodate
    journal, March 2004

    • Sullens, Tyler A.; Jensen, Rebecca A.; Shvareva, Tatiana Y.
    • Journal of the American Chemical Society, Vol. 126, Issue 9
    • DOI: 10.1021/ja031695h

    The Mechanism of Water Exchange in AmO 2 (H 2 O) 5 2+ and in the Isoelectronic UO 2 (H 2 O) 5 + and NpO 2 (H 2 O) 5 2+ Complexes as Studied by Quantum Chemical Methods
    journal, June 2004

    • Vallet, Valérie; Privalov, Timofei; Wahlgren, Ulf
    • Journal of the American Chemical Society, Vol. 126, Issue 25
    • DOI: 10.1021/ja0483544

    Influence of Countercation Hydration Enthalpies on the Formation of Molecular Complexes: A Thorium–Nitrate Example
    journal, November 2017

    • Jin, Geng Bang; Lin, Jian; Estes, Shanna L.
    • Journal of the American Chemical Society, Vol. 139, Issue 49
    • DOI: 10.1021/jacs.7b09363

    Uranyl to Uranium(IV) Conversion through Manipulation of Axial and Equatorial Ligands
    journal, February 2018

    • Bell, Nicola L.; Shaw, Brian; Arnold, Polly L.
    • Journal of the American Chemical Society, Vol. 140, Issue 9
    • DOI: 10.1021/jacs.7b13474

    Intensities in the Spectra of Actinyl Ions
    journal, December 2000

    • Matsika, Spiridoula; Pitzer, Russell M.; Reed, Donald T.
    • The Journal of Physical Chemistry A, Vol. 104, Issue 51
    • DOI: 10.1021/jp002580s

    Electronic Structure and Bonding in Actinyl Ions and their Analogs
    journal, May 2007

    • Denning, Robert G.
    • The Journal of Physical Chemistry A, Vol. 111, Issue 20
    • DOI: 10.1021/jp071061n

    Probing the Nature of Chemical Bonding in Uranyl(VI) Complexes with Quantum Chemical Methods
    journal, November 2012

    • Vallet, Valérie; Wahlgren, Ulf; Grenthe, Ingmar
    • The Journal of Physical Chemistry A, Vol. 116, Issue 50
    • DOI: 10.1021/jp3091123

    Reduction and selective oxo group silylation of the uranyl dication
    journal, January 2008

    • Arnold, Polly L.; Patel, Dipti; Wilson, Claire
    • Nature, Vol. 451, Issue 7176
    • DOI: 10.1038/nature06467

    Uranium and manganese assembled in a wheel-shaped nanoscale single-molecule magnet with high spin-reversal barrier
    journal, November 2012

    • Mougel, Victor; Chatelain, Lucile; Pécaut, Jacques
    • Nature Chemistry, Vol. 4, Issue 12
    • DOI: 10.1038/nchem.1494

    Redox-inactive metals modulate the reduction potential in heterometallic manganese–oxido clusters
    journal, March 2013

    • Tsui, Emily Y.; Tran, Rosalie; Yano, Junko
    • Nature Chemistry, Vol. 5, Issue 4
    • DOI: 10.1038/nchem.1578

    Crystal structure of a metal ion-bound oxoiron(IV) complex and implications for biological electron transfer
    journal, July 2010

    • Fukuzumi, Shunichi; Morimoto, Yuma; Kotani, Hiroaki
    • Nature Chemistry, Vol. 2, Issue 9
    • DOI: 10.1038/nchem.731

    Cation–cation interactions between NpO2+ and UO22+ at different temperatures and ionic strengths
    journal, January 2012

    • Xian, Liang; Tian, Guoxin; Zheng, Weifang
    • Dalton Transactions, Vol. 41, Issue 28
    • DOI: 10.1039/c2dt30736g

    Development and application of effective pairwise potentials for UO2n+, NpO2n+, PuO2n+, and AmO2n+ (n = 1, 2) ions with water
    journal, January 2013

    • Pomogaev, Vladimir; Tiwari, Surya Prakash; Rai, Neeraj
    • Physical Chemistry Chemical Physics, Vol. 15, Issue 38
    • DOI: 10.1039/c3cp52444b

    Electron-Transfer Kinetics of Np[sup 3+]∕Np[sup 4+], NpO[sub 2][sup +]∕NpO[sub 2][sup 2+], V[sup 2+]∕V[sup 3+], and VO[sup 2+]∕VO[sub 2][sup +] at Carbon Electrodes
    journal, January 2005

    • Yamamura, Tomoo; Watanabe, Nobutaka; Yano, Takashi
    • Journal of The Electrochemical Society, Vol. 152, Issue 4
    • DOI: 10.1149/1.1870794

    The Raman Scattering of Uranyl and Transuranium V, VI, and VII Ions
    journal, March 1974


      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.