Density Functional Theory Guided Investigation of Ligand‐Induced Neptunyl‐Neptunyl Interactions

Augustine, Logan J.; Pyrch, Mikaela Mary F.; Kravchuk, Dmytro V.; Williams, Jay M.; Mason, Sara E.; Forbes, Tori Z.

doi:10.1002/ejic.202200693

Density Functional Theory Guided Investigation of Ligand‐Induced Neptunyl‐Neptunyl Interactions

Journal Article · Wed Mar 22 00:00:00 EDT 2023 · European Journal of Inorganic Chemistry

DOI:https://doi.org/10.1002/ejic.202200693· OSTI ID:1963122

Augustine, Logan J. ^[1]; Pyrch, Mikaela Mary F. ^[1]; Kravchuk, Dmytro V. ^[1]; Williams, Jay M. ^[1]; Mason, Sara E. ^[1]; ^[1]

Department of Chemistry University of Iowa 52242 Iowa City IA USA

Abstract

Actinyl‐actinyl interactions are particularly prevalent for the pentavalent neptunyl cation (Np(V)O ₂ ) ⁺ where these interactions appear either as a T ‐ or D ‐shape (diamond‐shape). T ‐shaped interactions have been previously identified in high concentration Np(V) solutions containing simple anions (NO ₃ ⁻ , ClO ₄ ⁻ , Cl ⁻ ) whereas D ‐shaped have only been isolated in the solid‐state in the presence of carboxylate ligands. In this study, Density Functional Theory (DFT) calculations were paired with Raman spectroscopy to evaluate the formation of D ‐shaped interactions in the presence of aliphatic (R=H (formate), CH ₃ (acetate), CH ₂ CH ₃ (propionate)) and aromatic (R=C ₆ H ₅ (benzoate), C ₆ H ₄ OH (4‐hydroxybenzoate), C ₅ H ₄ N (isonicotinate)) carboxylate ligands. DFT studies indicate that the Δ G to form hydrated T ‐ and D ‐shaped forms are not spontaneous but become so with the addition of the carboxylate ligands. Raman spectra of the Np(V) carboxylate solutions contained vibrational modes associated with the D ‐shaped interactions, but spectral changes observed over time indicate a dynamic system. Crystallization experiments from the Np(V) carboxylate systems confirmed the presence of D‐ shaped dimers for the aromatic carboxylates, suggesting that the choice of the anion in solution favors actinyl‐actinyl interactions even at low concentrations (≤20 mM) of Np(V).

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Research Organization:: University of Iowa, Iowa City, IA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0021420

OSTI ID:: 1963122

Alternate ID(s):: OSTI ID: 2386947

Journal Information:: European Journal of Inorganic Chemistry, Journal Name: European Journal of Inorganic Chemistry Journal Issue: 14 Vol. 26; ISSN 1434-1948

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (44)

Synthesis and Characterization of the First 2 D Neptunyl Structure Stabilized by Side-on Cation-Cation Interactions Vlaisavljevich, Bess; Miró, Pere; Ma, Dongxia Chemistry - A European Journal, Vol. 19, Issue 9 https://doi.org/10.1002/chem.201204149	journal	January 2013
An efficient grid-based scheme to compute QTAIM atomic properties without explicit calculation of zero-flux surfaces Rodríguez, Juan I.; Köster, Andreas M.; Ayers, Paul W. Journal of Computational Chemistry, Vol. 30, Issue 7 https://doi.org/10.1002/jcc.21134	journal	May 2009
TmoleX-A graphical user interface for TURBOMOLE Steffen, Claudia; Thomas, Klaus; Huniar, Uwe Journal of Computational Chemistry https://doi.org/10.1002/jcc.21576	journal	January 2010
An efficient method for computing the QTAIM topology of a scalar field: The electron density case Rodríguez, Juan I. Journal of Computational Chemistry, Vol. 34, Issue 8 https://doi.org/10.1002/jcc.23180	journal	November 2012
Molecular oxides of high-valent actinides Kovács, Attila Structural Chemistry, Vol. 31, Issue 4 https://doi.org/10.1007/s11224-020-01555-3	journal	May 2020
Bader’s Theory of Atoms in Molecules (AIM) and its Applications to Chemical Bonding Kumar, P. Shyam Vinod; Raghavendra, V.; Subramanian, V. Journal of Chemical Sciences, Vol. 128, Issue 10 https://doi.org/10.1007/s12039-016-1172-3	journal	October 2016
“Cation-cation” complexes of pentavalent actinides—I Madic, C.; Guillaume, B.; Morisseau, J. C. Journal of Inorganic and Nuclear Chemistry, Vol. 41, Issue 7 https://doi.org/10.1016/0022-1902(79)80082-2	journal	January 1979
Crystal structure of a neptunyl cation-cation complex (NpO2+) with mellitic acid: Na4(NpO2)2Cl12O12·8H2O Cousson, Alain; Dabos, Sylvie; Abazli, Hicham Journal of the Less Common Metals, Vol. 99, Issue 2 https://doi.org/10.1016/0022-5088(84)90220-0	journal	June 1984
RI-MP2: optimized auxiliary basis sets and demonstration of efficiency Weigend, Florian; Häser, Marco; Patzelt, Holger Chemical Physics Letters, Vol. 294, Issue 1-3 https://doi.org/10.1016/S0009-2614(98)00862-8	journal	September 1998
Raman spectroscopy of neptunyl and plutonyl in aqueous solutions: hydrolysis of Np(VI) and Pu(VI) and disproportionation of Pu(V) Madic, C.; Begun, G. M.; Hobart, D. E. Inorganica Chimica Acta, Vol. 94, Issue 1-3 https://doi.org/10.1016/S0020-1693(00)94571-7	journal	February 1984
Oxo ligand functionalization in the uranyl ion (UO22+) Fortier, Skye; Hayton, Trevor W. Coordination Chemistry Reviews, Vol. 254, Issue 3-4 https://doi.org/10.1016/j.ccr.2009.06.003	journal	February 2010
The crystal and coordination chemistry of neptunium in all its oxidation states: An expanded structural hierarchy of neptunium compounds Gilson, Sara E.; Burns, Peter C. Coordination Chemistry Reviews, Vol. 445 https://doi.org/10.1016/j.ccr.2021.213994	journal	October 2021
A high performance grid-based algorithm for computing QTAIM properties Rodríguez, Juan I.; Bader, Richard F. W.; Ayers, Paul W. Chemical Physics Letters, Vol. 472, Issue 1-3 https://doi.org/10.1016/j.cplett.2009.02.081	journal	April 2009
Effect of temperature on the complexation of NpO2+ with benzoic acid: Spectrophotometric and calorimetric studies Yang, Yanqiu; Zhang, Zhicheng; Liu, Guokui The Journal of Chemical Thermodynamics, Vol. 80 https://doi.org/10.1016/j.jct.2014.08.022	journal	January 2015
Segmented contraction scheme for small-core actinide pseudopotential basis sets Cao, Xiaoyan; Dolg, Michael Journal of Molecular Structure: THEOCHEM, Vol. 673, Issue 1-3 https://doi.org/10.1016/j.theochem.2003.12.015	journal	March 2004
Thermodynamics and Structure of Neptunium(V) Complexes with Formate. Spectroscopic and Theoretical Study Maiwald, Martin M.; Dardenne, Kathy; Rothe, Jörg Inorganic Chemistry, Vol. 59, Issue 9 https://doi.org/10.1021/acs.inorgchem.0c00054	journal	April 2020
Three-Dimensional Network of Cation–Cation-Bound Neptunyl(V) Squares: Synthesis and in Situ Raman Spectroscopy Studies Jin, Geng Bang Inorganic Chemistry, Vol. 55, Issue 5 https://doi.org/10.1021/acs.inorgchem.5b02955	journal	February 2016
Recent Advances in Aqueous Actinide Chemistry and Thermodynamics Altmaier, Marcus; Gaona, Xavier; Fanghänel, Thomas Chemical Reviews, Vol. 113, Issue 2 https://doi.org/10.1021/cr300379w	journal	October 2012
Raman spectrometric studies of "cation-cation" complexes of pentavalent actinides in aqueous perchlorate solutions Guillaume, B.; Begun, G. M.; Hahn, R. L. Inorganic Chemistry, Vol. 21, Issue 3 https://doi.org/10.1021/ic00133a055	journal	March 1982
Investigations of "cation-cation" complexes of neptunyl ion (NpO2+) solutions by large-angle x-ray scattering Guillaume, B.; Hahn, R. L.; Narten, A. H. Inorganic Chemistry, Vol. 22, Issue 1 https://doi.org/10.1021/ic00143a024	journal	January 1983
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
Vibrational Spectroscopic Investigation of Benzoic Acid Adsorbed on Silver Kwon, Yong Joon; Son, Dong Hee; Ahn, Sang Jung The Journal of Physical Chemistry, Vol. 98, Issue 34 https://doi.org/10.1021/j100085a030	journal	August 1994
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
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
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
Polynuclear Cation−Cation Complexes of Pentavalent Uranyl: Relating Stability and Magnetic Properties to Structure Nocton, Grégory; Horeglad, Pawel; Pécaut, Jacques Journal of the American Chemical Society, Vol. 130, Issue 49 https://doi.org/10.1021/ja804766r	journal	December 2008
Electronic Structure and Bonding in Actinyl Ions and their Analogs Denning, Robert G. The Journal of Physical Chemistry A, Vol. 111, Issue 20 https://doi.org/10.1021/jp071061n	journal	May 2007
A Reliable and Efficient First Principles-Based Method for Predicting p K _a Values. 2. Organic Acids Zhang, Shuming; Baker, Jon; Pulay, Peter The Journal of Physical Chemistry A, Vol. 114, Issue 1 https://doi.org/10.1021/jp9067087	journal	January 2010
Elucidating cation–cation interactions in neptunyl dications using multi-reference ab initio theory Łachmańska, Aleksandra; Tecmer, Paweł; Legeza, Örs Physical Chemistry Chemical Physics, Vol. 21, Issue 2 https://doi.org/10.1039/C8CP04267E	journal	January 2019
Use of vibrational spectroscopy to identify the formation of neptunyl–neptunyl interactions: a paired density functional theory and Raman spectroscopy study Pyrch, Mikaela M.; Augustine, Logan J.; Williams, James M. Dalton Transactions, Vol. 51, Issue 12 https://doi.org/10.1039/D2DT00200K	journal	January 2022
Valence basis sets for relativistic energy-consistent small-core actinide pseudopotentials Cao, Xiaoyan; Dolg, Michael; Stoll, Hermann The Journal of Chemical Physics, Vol. 118, Issue 2 https://doi.org/10.1063/1.1521431	journal	January 2003
Gaussian‐2 theory for molecular energies of first‐ and second‐row compounds Curtiss, Larry A.; Raghavachari, Krishnan; Trucks, Gary W. The Journal of Chemical Physics, Vol. 94, Issue 11 https://doi.org/10.1063/1.460205	journal	June 1991
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
Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide Küchle, W.; Dolg, M.; Stoll, H. The Journal of Chemical Physics, Vol. 100, Issue 10 https://doi.org/10.1063/1.466847	journal	May 1994
TURBOMOLE: Modular program suite for ab initio quantum-chemical and condensed-matter simulations Balasubramani, Sree Ganesh; Chen, Guo P.; Coriani, Sonia The Journal of Chemical Physics, Vol. 152, Issue 18 https://doi.org/10.1063/5.0004635	journal	May 2020
Cation–cation interaction in crystalline actinide compounds Krot, Nikolai N.; Grigoriev, Mikhail S. Russian Chemical Reviews, Vol. 73, Issue 1 https://doi.org/10.1070/RC2004v073n01ABEH000852	journal	January 2004
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Dimeric dioxocations, (NpO ₂ ⁺ ) ₂ , in the structure of bis(μ-2-fluorobenzoato-κ ² O : O ′)di-μ-oxo-bis[(2,2′-bipyridine-κ ² N , N ′)oxoneptunium(V)] Grigoriev, Mikhail S.; Krot, Nikolai N.; Bessonov, Alexei A. Acta Crystallographica Section E Structure Reports Online, Vol. 63, Issue 2 https://doi.org/10.1107/S1600536807002164	journal	January 2007
Crystal structure of new complexes of Np(V) and Pu(V) propionates with 2,2’-bipyridine, [AnO2(C10H8N2)(OOCC2H5)(H2O)] Krot, N. N.; Charushnikova, I. A.; Grigor’ev, M. S. Radiochemistry, Vol. 52, Issue 1 https://doi.org/10.1134/S1066362210010030	journal	February 2010
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
Solvent effect on preferred protonation sites in nicotinate and isonicotinate anions Hallé, Jean-Claude; Lelievre, Jacques; Terrier, François Canadian Journal of Chemistry, Vol. 74, Issue 4 https://doi.org/10.1139/v96-065	journal	April 1996
Actinide Environmental Chemistry Silva, R. J.; Nitsche, H. Radiochimica Acta, Vol. 70-71, Issue s1 https://doi.org/10.1524/ract.1995.7071.special-issue.377	journal	January 1995
Cation–cation interaction in crystal structures of Np(V) and Pu(V) benzoate complexes with 2,2′-bipyridine, [NpO2(C10H8N2)(OOCC6H5)]2 and [PuO2(C10H8N2)(OOCC6H5)]2 Charushnikova, I. A.; Krot, N. N.; Starikova, Z. A. Radiochimica Acta, Vol. 95, Issue 9 https://doi.org/10.1524/ract.2007.95.9.495	journal	January 2007
Neptunyl Compounds: Polyhedron Geometries, Bond-Valence Parameters, and Structural Hierarchy Forbes, T. Z.; Wallace, C.; Burns, P. C. The Canadian Mineralogist, Vol. 46, Issue 6 https://doi.org/10.3749/canmin.46.6.1623	journal	December 2008

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