A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO2·M]4+ Cation–Cation Complexes

Freiderich, John W.; Burn, Adam G.; Martin, Leigh R.; Nash, Kenneth L.; Clark, Aurora E.

doi:10.1021/acs.inorgchem.6b02369

Title: A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO₂·M]⁴⁺ Cation–Cation Complexes

Journal Article · Fri Apr 14 00:00:00 EDT 2017 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.6b02369· OSTI ID:1356947

^[1]; Burn, Adam G. ^[1];

^[2]; Nash, Kenneth L. ^[1]; Clark, Aurora E. ^[1]

Washington State Univ., Pullman, WA (United States). Dept. of Chemistry
Idaho National Lab. (INL), Idaho Falls, ID (United States)

The equilibrium constants for [NpO₂M∙]⁴⁺ (M = Al³⁺, In³⁺, Sc³⁺, Fe³⁺) in μ = 10 M nitric acid and [NpO₂∙Ga]⁴⁺ in μ = 10 M hydrochloric acid media have been determined. The trend in the interaction strength follows: Fe³⁺ > Sc³⁺ In³⁺ > Ga³⁺ Al³⁺. These equilibrium constants are compared to those of previously reported values for NpO₂⁺ complexes with Cr³⁺ and Rh³⁺ within the literature. Thermodynamic parameters and bonding modes are discussed, with density functional theory and natural bond orbital analysis indicating that the NpO₂⁺ dioxocation acts as a -donor with transition-metal cations and a sigma donor with group 13 cations. The small changes in electron-donating ability is modulated by the overlap with the coordinating metal ion's valence atomic orbitals.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Washington State Univ., Pullman, WA (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE); USDOE Office of Science (SC)

Grant/Contract Number:: AC05-00OR22725; SC0001815

OSTI ID:: 1356947

Alternate ID(s):: OSTI ID: 1596319

Journal Information:: Inorganic Chemistry, Vol. 56, Issue 9; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 7 works

Citation information provided by
Web of Science

References (35)

Solvent Extraction of Np (V) with CMPO from Nitric Acid Solutions Containing U (VI) Nagasaki, Shinya; Kinoshita, Kouichi; Enokida, Youichi Journal of Nuclear Science and Technology, Vol. 29, Issue 11 https://doi.org/10.1080/18811248.1992.9731641	journal	November 1992
Chemical Properties of Neptunium Applied to Neptunium Management in Extraction Cycles of Purex Process Guillaume, B.; Moulin, J. P.; Maurice, Ch. Extraction '84 https://doi.org/10.1016/B978-0-08-031439-6.50006-4	book	January 1984
Specific Interaction between Np(V) and U(VI) in Aqueous Perchloric Acid Media ¹ Sullivan, J. C.; Hindman, J. C.; Zielen, A. J. Journal of the American Chemical Society, Vol. 83, Issue 16 https://doi.org/10.1021/ja01477a004	journal	August 1961
Complex Ion Formation between Cations. Spectra and Identification of a Np(V)-Cr(III) Complex Sullivan, James C. Journal of the American Chemical Society, Vol. 84, Issue 22 https://doi.org/10.1021/ja00881a012	journal	November 1962
The formation of a neptunium(V)-rhodium(III) complex. Kinetics and equilibriums in acidic solutions Murmann, R. Kent; Sullivan, James Charles Inorganic Chemistry, Vol. 6, Issue 5 https://doi.org/10.1021/ic50051a008	journal	May 1967
The Formation of a Neptunium(V)-Chromium(III) Complex. Kinetics and Equilibria in Perchlorate Solutions Sullivan, James C. Inorganic Chemistry, Vol. 3, Issue 3 https://doi.org/10.1021/ic50013a002	journal	March 1964
Dimerization of aquadioxovanadium(V) ion in concentrated perchloric and sulfuric acid media Madic, C.; Begun, G. M.; Hahn, R. L. Inorganic Chemistry, Vol. 23, Issue 4 https://doi.org/10.1021/ic00172a019	journal	February 1984
Formation and properties of a stable heterobinuclear complex containing ruthenium and vanadium De Smedt, Humbert.; Persoons, Andre.; De Maeyer, Leo. Inorganic Chemistry, Vol. 13, Issue 1 https://doi.org/10.1021/ic50131a017	journal	January 1974
Study of Hg ₂ ²⁺ and Complexes of NpO ₂ ⁺ and UO ₂ ²⁺ in Solution. Examples of Cation−Cation Interactions McKee, Michael L.; Swart, Marcel Inorganic Chemistry, Vol. 44, Issue 20 https://doi.org/10.1021/ic050224o	journal	October 2005
Separation and preconcentration of actinides from acidic media by extraction chromatography Horwitz, E. Philip; Chiarizia, Renato; Dietz, Mark L. Analytica Chimica Acta, Vol. 281, Issue 2 https://doi.org/10.1016/0003-2670(93)85194-O	journal	September 1993
The Chemistry of the Actinide and Transactinide Elements Morss, Lester R.; Edelstein, Norman M.; Fuger, Jean https://doi.org/10.1007/1-4020-3598-5	book	January 2006
Symmetry, Optical Properties and Thermodynamics of Neptunium(V) Complexes Rao, Linfeng; Tian, Guoxin Symmetry, Vol. 2, Issue 1 https://doi.org/10.3390/sym2010001	journal	December 2009
Electronic Spectrum of the NpO ₂ ²⁺ and NpO ₂ ⁺ Ions Matsika, Spiridoula; Pitzer, Russell M. The Journal of Physical Chemistry A, Vol. 104, Issue 17 https://doi.org/10.1021/jp993767q	journal	May 2000
Investigation of equilibria in solution. Determination of equilibrium constants with the HYPERQUAD suite of programs Gans, P.; Sabatini, A.; Vacca, A. Talanta, Vol. 43, Issue 10 https://doi.org/10.1016/0039-9140(96)01958-3	journal	October 1996
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F. The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627 https://doi.org/10.1021/j100096a001	journal	November 1994
Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis Vosko, S. H.; Wilk, L.; Nusair, M. Canadian Journal of Physics, Vol. 58, Issue 8 https://doi.org/10.1139/p80-159	journal	August 1980
Systematically convergent basis sets for transition metals. I. All-electron correlation consistent basis sets for the 3d elements Sc–Zn Balabanov, Nikolai B.; Peterson, Kirk A. The Journal of Chemical Physics, Vol. 123, Issue 6 https://doi.org/10.1063/1.1998907	journal	August 2005
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen Dunning, Thom H. The Journal of Chemical Physics, Vol. 90, Issue 2 https://doi.org/10.1063/1.456153	journal	January 1989
Gaussian basis sets for use in correlated molecular calculations. IX. The atoms gallium through krypton Wilson, Angela K.; Woon, David E.; Peterson, Kirk A. The Journal of Chemical Physics, Vol. 110, Issue 16 https://doi.org/10.1063/1.478678	journal	April 1999
Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon Woon, David E.; Dunning, Thom H. The Journal of Chemical Physics, Vol. 98, Issue 2 https://doi.org/10.1063/1.464303	journal	January 1993
Relativistic and correlation effects for element 105 (hahnium, Ha): a comparative study of M and MO (M = Nb, Ta, Ha) using energy-adjusted ab initio pseudopotentials Dolg, Michael; Stoll, Hermann; Preuss, Heinzwerner The Journal of Physical Chemistry, Vol. 97, Issue 22 https://doi.org/10.1021/j100124a012	journal	June 1993
Systematically convergent basis sets with relativistic pseudopotentials. I. Correlation consistent basis sets for the post- d group 13–15 elements Peterson, Kirk A. The Journal of Chemical Physics, Vol. 119, Issue 21 https://doi.org/10.1063/1.1622923	journal	December 2003
Sensitivity of Solvation Environment to Oxidation State and Position in the Early Actinide Period Clark, Aurora E.; Samuels, Alex; Wisuri, Katy Inorganic Chemistry, Vol. 54, Issue 13 https://doi.org/10.1021/acs.inorgchem.5b00365	journal	June 2015
Gas-Phase Uranyl, Neptunyl, and Plutonyl: Hydration and Oxidation Studied by Experiment and Theory Rios, Daniel; Michelini, Maria C.; Lucena, Ana F. Inorganic Chemistry, Vol. 51, Issue 12 https://doi.org/10.1021/ic3001625	journal	June 2012
UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations Rappe, A. K.; Casewit, C. J.; Colwell, K. S. Journal of the American Chemical Society, Vol. 114, Issue 25, p. 10024-10035 https://doi.org/10.1021/ja00051a040	journal	December 1992
Applications of Polarizable Continuum Models To Determine Accurate Solution-Phase Thermochemical Values Across a Broad Range of Cation Charge – The Case of U(III–VI) Parmar, Payal; Samuels, Alex; Clark, Aurora E. Journal of Chemical Theory and Computation, Vol. 11, Issue 1 https://doi.org/10.1021/ct500530q	journal	December 2014
Natural population analysis Reed, Alan E.; Weinstock, Robert B.; Weinhold, Frank The Journal of Chemical Physics, Vol. 83, Issue 2 https://doi.org/10.1063/1.449486	journal	July 1985
The role of inner-sphere configuration changes in electron-exchange reactions of metal complexes Brunschwig, Bruce S.; Creutz, Carol; Macartney, Donal H. Faraday Discussions of the Chemical Society, Vol. 74 https://doi.org/10.1039/dc9827400113	journal	January 1982
Order phenomena in aqueous AlCl ₃ solutions Caminiti, R.; Licheri, G.; Piccaluga, G. The Journal of Chemical Physics, Vol. 71, Issue 6 https://doi.org/10.1063/1.438654	journal	September 1979
The Structure of the Hydrated Gallium(III), Indium(III), and Chromium(III) Ions in Aqueous Solution. A Large Angle X-ray Scattering and EXAFS Study Lindqvist-Reis, Patric; Muñoz-Páez, Adela; Díaz-Moreno, Sofia Inorganic Chemistry, Vol. 37, Issue 26 https://doi.org/10.1021/ic980750y	journal	December 1998
Hydrolysis of Ferric Ion in Water and Conformational Equilibrium Martin, Richard L.; Hay, P. Jeffrey; Pratt, Lawrence R. The Journal of Physical Chemistry A, Vol. 102, Issue 20 https://doi.org/10.1021/jp980229p	journal	May 1998
X-ray Diffraction Study on Aqueous Scandium(III) Perchlorate and Chloride Solutions over the Temperature Range −45 to 95 °C Smirnov, Pavel; Wakita, Hisanobu; Yamaguchi, Toshio The Journal of Physical Chemistry B, Vol. 102, Issue 24 https://doi.org/10.1021/jp980075d	journal	May 1998
Neptunium redox speciation Antonio, R.; Soderholm, L.; Williams, C. W. Radiochimica Acta, Vol. 89, Issue 1 https://doi.org/10.1524/ract.2001.89.1.017	journal	January 2001
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976

Cited By (2)

Impacts of hydrogen bonding interactions with Np( v / vi )O ₂ Cl ₄ complexes: vibrational spectroscopy, redox behavior, and computational analysis Pyrch, Mikaela M.; Bjorklund, Jennifer L.; Williams, James M. Dalton Transactions, Vol. 49, Issue 20 https://doi.org/10.1039/d0dt00848f	journal	January 2020
Ion association with tetra-n-alkylammonium cations stabilizes higher-oxidation-state neptunium dioxocations Estes, Shanna L.; Qiao, Baofu; Jin, Geng Bang Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-018-07982-5	journal	January 2019

Similar Records

Crystal structure of Cs/sub 4/(NpO/sub 2/)/sub 3/Cl/sub 6/(NO/sub 3/)H/sub 2/O: structure of the polymer with NpO/sub 2//sup +/-NpO/sub 2//sup +/ cation interaction

Journal Article · Thu Jan 01 00:00:00 EST 1987 · Sov. Radiochem. (Engl. Transl.); (United States) · OSTI ID:1356947

Tomilin, S V; Volkov, Yu F; Melkaya, R F; +2 more

Pentavalent neptunyl ([OΞNpΞO]⁺) cation–cation interactions in aqueous/polar organic mixed-solvent media

Journal Article · Sat Jun 17 00:00:00 EDT 2017 · Journal of Solution Chemistry · OSTI ID:1356947

Burn, Adam G.; Martin, Leigh R.; Nash, Kenneth L.

Synthesis conditions and thermal parameters for Cs/sub 4/((NpO/sub 2/)/sub 3/Cl/sub 6/NO/sub 3/H/sub 2/O)

Journal Article · Thu Jan 01 00:00:00 EST 1987 · Sov. Radiochem. (Engl. Transl.); (United States) · OSTI ID:1356947

Volkov, Yu F; Melkaya, R F; Spiryakov, V I; +2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
cation-cation
neptunium
high ionic strength
spectrophotometry
density functional theory

Title: A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO2·M]4+ Cation–Cation Complexes

Citation Formats

References (35)

Cited By (2)

Similar Records

Related Subjects

Title: A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO₂·M]⁴⁺ Cation–Cation Complexes