Strengthening of the Coordination Shell by Counter Ions in Aqueous Th 4+ Solutions

Atta-Fynn, Raymond; Bylaska, Eric J.; de Jong, Wibe A.

doi:10.1021/acs.jpca.6b09878

Strengthening of the Coordination Shell by Counter Ions in Aqueous Th ⁴⁺ Solutions

Journal Article · Wed Dec 28 23:00:00 EST 2016 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.6b09878· OSTI ID:1343177

Atta-Fynn, Raymond; Bylaska, Eric J.;

The presence of counter ions in solutions containing highly charged metal cations can trigger processes such as ion-pair formation, hydrogen bond breakages and subsequent reformation, and ligand exchanges. In this work, it is shown how halide (Cl-, Br-) and perchlorate (ClO4-) anions affect the strength of the primary solvent coordination shells around Th4+ using explicit solvent and finite temperature ab initio molecular dynamics modeling methods. The 9-fold solvent geometry was found to be the most stable hydration structure in each aqueous solution. Relative to the dilute aqueous solution, the presence of the counter ions did not significantly alter the geometry of the primary hydration shell. However, the free energy analyses indicated that the 10-fold hydrated states were thermodynamically accessible in dilute and bromide aqueous solutions within 1 kcal/mol. Analysis of the results showed that the hydrogen bond lifetimes were longer and solvent exchange energy barriers were larger in solutions with counter ions in comparison with the solution with no counter ions. This implies that the presence of the counter ions induces a strengthening of the Th4+ hydration shell.

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1343177

Report Number(s):: PNNL-SA--122830; KP1704020

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 51 Vol. 120; ISSN 1089-5639

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

References (38)

Unified Approach for Molecular Dynamics and Density-Functional Theory Car, R.; Parrinello, M. Physical Review Letters, Vol. 55, Issue 22 https://doi.org/10.1103/PhysRevLett.55.2471	journal	November 1985
Quantum Chemical and Molecular Dynamics Study of the Coordination of Th(IV) in Aqueous Solvent Réal, Florent; Trumm, Michael; Vallet, Valérie The Journal of Physical Chemistry B, Vol. 114, Issue 48 https://doi.org/10.1021/jp108061s	journal	December 2010
Structure and Dynamics of Liquid Water from ab Initio Molecular Dynamics—Comparison of BLYP, PBE, and revPBE Density Functionals with and without van der Waals Corrections Lin, I-Chun; Seitsonen, Ari P.; Tavernelli, Ivano Journal of Chemical Theory and Computation, Vol. 8, Issue 10 https://doi.org/10.1021/ct3001848	journal	March 2012
XAFS Investigation of the Structure of Aqueous Thorium(IV) Species, Colloids, and Solid Thorium(IV) Oxide/Hydroxide Rothe, J.; Denecke, M. A.; Neck, V. Inorganic Chemistry, Vol. 41, Issue 2 https://doi.org/10.1021/ic010579h	journal	January 2002
Molecular Simulation Analysis and X-ray Absorption Measurement of Ca ²⁺ , K ⁺ and Cl ^- Ions in Solution Dang, Liem X.; Schenter, Gregory K.; Glezakou, Vassiliki-Alexandra The Journal of Physical Chemistry B, Vol. 110, Issue 47 https://doi.org/10.1021/jp064661f	journal	November 2006
Structural and electronic properties of aqueous NaCl solutions from ab initio molecular dynamics simulations with hybrid density functionals Gaiduk, Alex P.; Zhang, Cui; Gygi, François Chemical Physics Letters, Vol. 604 https://doi.org/10.1016/j.cplett.2014.04.037	journal	June 2014
Effect of Environment on Hydrogen Bond Dynamics in Liquid Water Luzar, Alenka; Chandler, David Physical Review Letters, Vol. 76, Issue 6 https://doi.org/10.1103/PhysRevLett.76.928	journal	February 1996
Hydration properties of Cm(iii) and Th(iv) combining coordination free energy profiles with electronic structure analysis Spezia, Riccardo; Jeanvoine, Yannick; Beuchat, Cesar Physical Chemistry Chemical Physics, Vol. 16, Issue 12 https://doi.org/10.1039/c3cp54958e	journal	January 2014
Quantum Mechanical and Molecular Dynamical Simulations on Thorium(IV) Hydrates in Aqueous Solution Yang, Tianxiao; Tsushima, Satoru; Suzuki, Atsuyuki The Journal of Physical Chemistry A, Vol. 105, Issue 45 https://doi.org/10.1021/jp012387d	journal	November 2001
Actinide speciation using X-ray absorption fine structure spectroscopy Denecke, M. Coordination Chemistry Reviews, Vol. 250, Issue 7-8 https://doi.org/10.1016/j.ccr.2005.09.004	journal	April 2006
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
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
Structure and hydrogen bond dynamics of water–dimethyl sulfoxide mixtures by computer simulations Luzar, Alenka; Chandler, David The Journal of Chemical Physics, Vol. 98, Issue 10 https://doi.org/10.1063/1.464521	journal	May 1993
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations Valiev, M.; Bylaska, E. J.; Govind, N. Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489 https://doi.org/10.1016/j.cpc.2010.04.018	journal	September 2010
Theory and Molecular Models for Water Stillinger, Frank H. Advances in Chemical Physics: Non‐Simple Liquids https://doi.org/10.1002/9780470143834.ch1	book	January 1975
Single-sweep methods for free energy calculations Maragliano, Luca; Vanden-Eijnden, Eric The Journal of Chemical Physics, Vol. 128, Issue 18 https://doi.org/10.1063/1.2907241	journal	May 2008
Importance of Counteranions on the Hydration Structure of the Curium Ion Atta-Fynn, Raymond; Bylaska, Eric J.; de Jong, Wibe A. The Journal of Physical Chemistry Letters, Vol. 4, Issue 13 https://doi.org/10.1021/jz400887a	journal	June 2013
EXAFS Investigation of U(VI), U(IV), and Th(IV) Sulfato Complexes in Aqueous Solution Hennig, Christoph; Schmeide, Katja; Brendler, Vinzenz Inorganic Chemistry, Vol. 46, Issue 15 https://doi.org/10.1021/ic0619759	journal	July 2007
Unravelling the Hydration Structure of ThX ₄ (X = Br, Cl) Water Solutions by Molecular Dynamics Simulations and X-ray Absorption Spectroscopy Spezia, Riccardo; Beuchat, Cesar; Vuilleumier, Rodolphe The Journal of Physical Chemistry B, Vol. 116, Issue 22 https://doi.org/10.1021/jp210350b	journal	May 2012
Resolving the hydrogen bond dynamics conundrum Luzar, Alenka The Journal of Chemical Physics, Vol. 113, Issue 23 https://doi.org/10.1063/1.1320826	journal	December 2000
Hydration and Hydrolysis of Thorium(IV) in Aqueous Solution and the Structures of Two Crystalline Thorium(IV) Hydrates Torapava, Natallia; Persson, Ingmar; Eriksson, Lars Inorganic Chemistry, Vol. 48, Issue 24 https://doi.org/10.1021/ic901763s	journal	December 2009
Coordination numbers as reaction coordinates in constrained molecular dynamics Sprik, Michiel Faraday Discussions, Vol. 110 https://doi.org/10.1039/a801517a	journal	January 1998
Metadynamics: a method to simulate rare events and reconstruct the free energy in biophysics, chemistry and material science Laio, Alessandro; Gervasio, Francesco L. Reports on Progress in Physics, Vol. 71, Issue 12 https://doi.org/10.1088/0034-4885/71/12/126601	journal	November 2008
Structure of the Homoleptic Thorium(IV) Aqua Ion [Th(H2O)10]Br4 Wilson, Richard E.; Skanthakumar, S.; Burns, Peter C. Angewandte Chemie International Edition, Vol. 46, Issue 42 https://doi.org/10.1002/anie.200702872	journal	October 2007
Effects of Ion Atmosphere on Hydrogen-Bond Dynamics in Aqueous Electrolyte Solutions Chandra, Amalendu Physical Review Letters, Vol. 85, Issue 4 https://doi.org/10.1103/PhysRevLett.85.768	journal	July 2000
Coordination around thorium(IV) in aqueous perchlorate, chloride and nitrate solutions Johansson, Georg; Magini, Mauro; Ohtaki, Hitoshi Journal of Solution Chemistry, Vol. 20, Issue 8 https://doi.org/10.1007/BF00675110	journal	August 1991
Density-functional exchange-energy approximation with correct asymptotic behavior Becke, A. D. Physical Review A, Vol. 38, Issue 6 https://doi.org/10.1103/PhysRevA.38.3098	journal	September 1988
Fast and Slow Dynamics of Hydrogen Bonds in Liquid Water Starr, Francis W.; Nielsen, Johannes K.; Stanley, H. Eugene Physical Review Letters, Vol. 82, Issue 11 https://doi.org/10.1103/PhysRevLett.82.2294	journal	March 1999
Escaping free-energy minima Laio, A.; Parrinello, M. Proceedings of the National Academy of Sciences, Vol. 99, Issue 20 https://doi.org/10.1073/pnas.202427399	journal	September 2002
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/PhysRev.140.A1133	journal	November 1965
Hydrogen bonds in water: Network organization and lifetimes Rapaport, D. C. Molecular Physics, Vol. 50, Issue 5 https://doi.org/10.1080/00268978300102931	journal	December 1983
Structure of the Aqua Ions and Fluoride Complexes of Uranium(IV) and Thorium(IV) in Aqueous Solution an EXAFS Study Moll, H.; Denecke, M. A.; Jalilehvand, F. Inorganic Chemistry, Vol. 38, Issue 8 https://doi.org/10.1021/ic981362z	journal	April 1999
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Applications of lanthanide luminescence spectroscopy to solution studies of coordination chemistry Choppin, Gregory R.; Peterman, Dean R. Coordination Chemistry Reviews, Vol. 174, Issue 1 https://doi.org/10.1016/S0010-8545(98)00125-8	journal	July 1998
Parameter-free calculations of X-ray spectra with FEFF9 Rehr, John J.; Kas, Joshua J.; Vila, Fernando D. Physical Chemistry Chemical Physics, Vol. 12, Issue 21 https://doi.org/10.1039/b926434e	journal	January 2010
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Chloride concentration and temperature effects on the hydration of Th(IV) ion: a molecular dynamics simulation Yang, Tianxiao; Tsushima, Satoru; Suzuki, Atsuyuki Chemical Physics Letters, Vol. 360, Issue 5-6 https://doi.org/10.1016/S0009-2614(02)00894-1	journal	July 2002
Actinides in Solution: Complexation and Kinetics Choppin, Gregory R.; Jensen, Mark P. The Chemistry of the Actinide and Transactinide Elements https://doi.org/10.1007/1-4020-3598-5_23	book	January 2007

Cited By (2)

Properties of the tetravalent actinide series in aqueous phase from a microscopic simulation self-consistent engine Acher, Eléonor; Masella, Michel; Vallet, Valérie Physical Chemistry Chemical Physics, Vol. 22, Issue 4 https://doi.org/10.1039/c9cp04912f	journal	January 2020
Density Functional Theory Investigations on the Mechanism of Formation of Pa(V) Ion in Hydrous Solutions Ma, Jun; Yang, Chuting; Han, Jun Molecules, Vol. 24, Issue 6 https://doi.org/10.3390/molecules24061169	journal	March 2019

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