Structure and water exchange dynamics of hydrated oxo halo ions in aqueous solution using QMCF MD simulation, large angle X-ray scattering and EXAFS

Eklund, Lars; Hofer, Tomas S.; Persson, Ingmar

doi:10.1039/c4dt02580f

Structure and water exchange dynamics of hydrated oxo halo ions in aqueous solution using QMCF MD simulation, large angle X-ray scattering and EXAFS

Journal Article · Wed Nov 26 00:00:00 EST 2014 · Dalton Transactions

DOI:https://doi.org/10.1039/c4dt02580f· OSTI ID:1346974

Eklund, Lars ^[1]; Hofer, Tomas S. ^[2]; Persson, Ingmar ^[3]

Univ. of Agricultural Sciences, Uppsala (Sweden); DOE Office of Scientific and Technical Information (OSTI)
Univ. of Innsbruck, Innsbruck (Austria)
Univ. of Agricultural Sciences, Uppsala (Sweden)

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) has been applied in conjunction with experimental large angle X-ray scattering (LAXS) and EXAFS measurements to study structure and dynamics of the hydrated oxo chloro anions chlorite, ClO₂^–, chlorate, ClO₃^–, and perchlorate, ClO₄^–. In addition, the structures of the hydrated hypochlorite, ClO^–, bromate, BrO₃^–, iodate, IO₃^– and metaperiodate, IO₄^–, ions have been determined in aqueous solution by means of LAXS. The structures of the bromate, metaperiodate, and orthoperiodate, H₂IO₆^3–, ions have been determined by EXAFS as solid sodium salts and in aqueous solution as well. The results show clearly that the only form of periodate present in aqueous solution is metaperiodate. The Cl–O bond distances in the hydrated oxo chloro anions as determined by LAXS and obtained in the QMCF MD simulations are in excellent agreement, being 0.01–0.02 Å longer than in solid anhydrous salts due to hydration through hydrogen bonding to water molecules. The oxo halo anions, all with unit negative charge, have low charge density making them typical structure breakers, thus the hydrogen bonds formed to the hydrating water molecules are weaker and more short-lived than those between water molecules in pure water. The water exchange mechanism of the oxo chloro anions resembles those of the oxo sulfur anions with a direct exchange at the oxygen atoms for perchlorate and sulfate. Here, the water exchange rate for the perchlorate ion is significantly faster, τ_0.5 = 1.4 ps, compared to the hydrated sulfate ion and pure water, τ_0.5 = 2.6 and 1.7 ps, respectively. The angular radial distribution functions show that the chlorate and sulfite ions have a more complex water exchange mechanism. As the chlorite and chlorate ions are more weakly hydrated than the sulfite ion the spatial occupancy is less well-defined and it is not possible to follow any well-defined migration pattern as it is difficult to distinguish between hydrating water molecules and bulk water in the region close to the ions.

View Accepted Manuscript (DOE)

Research Organization:: Stanford Univ., Stanford, CA (United States)

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

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1346974

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 4 Vol. 44; ISSN 1477-9226; ISSN ICHBD9

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (46)

Characterization of dynamics and reactivities of solvated ions byab initio simulations Hofer, Thomas S.; Tran, Hung T.; Schwenk, Christian F. Journal of Computational Chemistry, Vol. 25, Issue 2 https://doi.org/10.1002/jcc.10374	journal	January 2003
Structure and dynamics of phosphate ion in aqueous solution: An ab initio QMCF MD study Pribil, Andreas B.; Hofer, Thomas S.; Randolf, Bernhard R. Journal of Computational Chemistry, Vol. 29, Issue 14 https://doi.org/10.1002/jcc.20968	journal	November 2008
A combined quantum mechanical and molecular mechanical potential for molecular dynamics simulations Field, Martin J.; Bash, Paul A.; Karplus, Martin Journal of Computational Chemistry, Vol. 11, Issue 6 https://doi.org/10.1002/jcc.540110605	journal	July 1990
Ab initio quantum mechanical charge field (QMCF) molecular dynamics: a QM/MM – MD procedure for accurate simulations of ions and complexes Rode, Bernd M.; Hofer, Thomas S.; Randolf, Bernhard R. Theoretical Chemistry Accounts, Vol. 115, Issue 2-3 https://doi.org/10.1007/s00214-005-0049-1	journal	December 2005
QM/MM: what have we learned, where are we, and where do we go from here? Lin, Hai; Truhlar, Donald G. Theoretical Chemistry Accounts, Vol. 117, Issue 2 https://doi.org/10.1007/s00214-006-0143-z	journal	July 2006
An improved potential for non-rigid water molecules in the liquid phase Bopp, P.; Jancsó, G.; Heinzinger, K. Chemical Physics Letters, Vol. 98, Issue 2 https://doi.org/10.1016/0009-2614(83)87112-7	journal	June 1983
Electronic structure calculations on workstation computers: The program system turbomole Ahlrichs, Reinhart; Bär, Michael; Häser, Marco Chemical Physics Letters, Vol. 162, Issue 3 https://doi.org/10.1016/0009-2614(89)85118-8	journal	October 1989
Theoretical studies of enzymic reactions: Dielectric, electrostatic and steric stabilization of the carbonium ion in the reaction of lysozyme Warshel, A.; Levitt, M. Journal of Molecular Biology, Vol. 103, Issue 2 https://doi.org/10.1016/0022-2836(76)90311-9	journal	May 1976
VMD: Visual molecular dynamics Humphrey, William; Dalke, Andrew; Schulten, Klaus Journal of Molecular Graphics, Vol. 14, Issue 1 https://doi.org/10.1016/0263-7855(96)00018-5	journal	February 1996
Water exchange on metal ions: experiments and simulations Helm, L.; Merbach, A. E. Coordination Chemistry Reviews, Vol. 187, Issue 1 https://doi.org/10.1016/S0010-8545(99)90232-1	journal	June 1999
Ab Initio Quantum Mechanical Charge Field Molecular Dynamics—A Nonparametrized First-Principle Approach to Liquids and Solutions Hofer, Thomas S.; Pribil, Andreas B.; Randolf, Bernhard R. Advances in Quantum Chemistry https://doi.org/10.1016/S0065-3276(10)59007-5	book	January 2010
Simulations of Liquids and Solutions Based on Quantum Mechanical Forces Hofer, Thomas S.; Rode, Bernd M.; Pribil, Andreas B. Advances in Inorganic Chemistry https://doi.org/10.1016/S0898-8838(10)62004-1	book	January 2010
QM/MM studies of enzymes Senn, Hans Martin; Thiel, Walter Current Opinion in Chemical Biology, Vol. 11, Issue 2 https://doi.org/10.1016/j.cbpa.2007.01.684	journal	April 2007
Coordination and ligand exchange dynamics of solvated metal ions Rode, B. M.; Schwenk, C. F.; Hofer, T. S. Coordination Chemistry Reviews, Vol. 249, Issue 24 https://doi.org/10.1016/j.ccr.2005.03.032	journal	December 2005
Characteristics of selenate in aqueous solution – An ab initio QMCF-MD study Sakwarathorn, Theerathad; Pongstabodee, Sangobtip; Vchirawongkwin, Viwat Chemical Physics Letters, Vol. 595-596 https://doi.org/10.1016/j.cplett.2014.01.046	journal	March 2014
Structure and dynamics of hydrated ions Ohtaki, Hitoshi.; Radnai, Tamas. Chemical Reviews, Vol. 93, Issue 3 https://doi.org/10.1021/cr00019a014	journal	May 1993
The prehistory of the Belousov-Zhabotinsky oscillator Winfree, A. T. Journal of Chemical Education, Vol. 61, Issue 8 https://doi.org/10.1021/ed061p661	journal	August 1984
Structure and Dynamics of the Chromate Ion in Aqueous Solution. An ab Initio QMCF-MD Simulation Hinteregger, Ernst; Pribil, Andreas B.; Hofer, Thomas S. Inorganic Chemistry, Vol. 49, Issue 17 https://doi.org/10.1021/ic101001e	journal	September 2010
Coordination Chemistry Study of Hydrated and Solvated Lead(II) Ions in Solution and Solid State Persson, Ingmar; Lyczko, Krzysztof; Lundberg, Daniel Inorganic Chemistry, Vol. 50, Issue 3 https://doi.org/10.1021/ic1017714	journal	February 2011
A Study of the Hydration of the Alkali Metal Ions in Aqueous Solution Mähler, Johan; Persson, Ingmar Inorganic Chemistry, Vol. 51, Issue 1 https://doi.org/10.1021/ic2018693	journal	December 2011
Structure of the Solvated Zinc(II), Cadmium(II), and Mercury(II) Ions in N , N -Dimethylthioformamide Solution Stålhandske, Christina M. V.; Persson, Ingmar; Sandström, Magnus Inorganic Chemistry, Vol. 36, Issue 14 https://doi.org/10.1021/ic961339i	journal	July 1997
The missing term in effective pair potentials Berendsen, H. J. C.; Grigera, J. R.; Straatsma, T. P. The Journal of Physical Chemistry, Vol. 91, Issue 24 https://doi.org/10.1021/j100308a038	journal	November 1987
Potential of mean force for the isomerization of DMF in aqueous solution: a Monte Carlo QM/MM simulation study Gao, Jiali Journal of the American Chemical Society, Vol. 115, Issue 7 https://doi.org/10.1021/ja00060a047	journal	April 1993
Hydration of the Calcium Ion. An EXAFS, Large-Angle X-ray Scattering, and Molecular Dynamics Simulation Study Jalilehvand, Farideh; Spångberg, Daniel; Lindqvist-Reis, Patric Journal of the American Chemical Society, Vol. 123, Issue 3 https://doi.org/10.1021/ja001533a	journal	January 2001
Ionic Hydration Behavior Derived from Infrared Spectra in HDO Stangret, Janusz; Gampe, Teresa The Journal of Physical Chemistry A, Vol. 106, Issue 21 https://doi.org/10.1021/jp014063v	journal	May 2002
Structure and Dynamics of Sulfate Ion in Aqueous SolutionAn ab initio QMCF MD Simulation and Large Angle X-ray Scattering Study Vchirawongkwin, Viwat; Rode, Bernd M.; Persson, Ingmar The Journal of Physical Chemistry B, Vol. 111, Issue 16 https://doi.org/10.1021/jp0702402	journal	April 2007
QM/MM MD Simulations of Iodide Ion (I ⁻ ) in Aqueous Solution: A Delicate Balance between Ion−Water and Water−Water H-Bond Interactions Tongraar, Anan; Hannongbua, Supot; Rode, Bernd Michael The Journal of Physical Chemistry A, Vol. 114, Issue 12 https://doi.org/10.1021/jp910435d	journal	April 2010
Hybrid Models for Combined Quantum Mechanical and Molecular Mechanical Approaches Bakowies, Dirk; Thiel, Walter The Journal of Physical Chemistry, Vol. 100, Issue 25 https://doi.org/10.1021/jp9536514	journal	January 1996
ONIOM: A Multilayered Integrated MO + MM Method for Geometry Optimizations and Single Point Energy Predictions. A Test for Diels−Alder Reactions and Pt(P( t -Bu) ₃ ) ₂ + H ₂ Oxidative Addition Svensson, Mats; Humbel, Stéphane; Froese, Robert D. J. The Journal of Physical Chemistry, Vol. 100, Issue 50 https://doi.org/10.1021/jp962071j	journal	January 1996
Hydration of arsenic oxyacid species Mähler, Johan; Persson, Ingmar; Herbert, Roger B. Dalton Trans., Vol. 42, Issue 5 https://doi.org/10.1039/C2DT31906C	journal	January 2013
Exploiting the capabilities of quantum chemical simulations to characterise the hydration of molecular compounds Weiss, Alexander K. H.; Hofer, Thomas S. RSC Adv., Vol. 3, Issue 6 https://doi.org/10.1039/C2RA21873A	journal	January 2013
Structure and hydrogen bonding of the hydrated selenite and selenate ions in aqueous solution Eklund, Lars; Persson, Ingmar Dalton Trans., Vol. 43, Issue 17 https://doi.org/10.1039/C3DT53468E	journal	January 2014
Structure and water exchange of the hydrated thiosulfate ion in aqueous solution using QMCF MD simulation and large angle X-ray scattering Eklund, Lars; Hofer, Tomas S.; Weiss, Alexander K. H. Dalton Trans., Vol. 43, Issue 33 https://doi.org/10.1039/C4DT01010H	journal	January 2014
On the structure and dynamics of the hydrated sulfite ion in aqueous solution – an ab initio QMCF MD simulation and large angle X-ray scattering study Eklund, Lars; Hofer, Thomas S.; Pribil, Andreas B. Dalton Transactions, Vol. 41, Issue 17 https://doi.org/10.1039/c2dt12467j	journal	January 2012
Compton Scattering Factors for Aspherical Free Atoms Cromer, Don T. The Journal of Chemical Physics, Vol. 50, Issue 11 https://doi.org/10.1063/1.1670980	journal	June 1969
Gaussian Basis Functions for Use in Molecular Calculations. I. Contraction of (9s5p) Atomic Basis Sets for the First‐Row Atoms Dunning, Thom H. The Journal of Chemical Physics, Vol. 53, Issue 7 https://doi.org/10.1063/1.1674408	journal	October 1970
Compton Scattering Factors for Spherically Symmetric Free Atoms Cromer, Don T.; Mann, Joseph B. The Journal of Chemical Physics, Vol. 47, Issue 6 https://doi.org/10.1063/1.1712213	journal	September 1967
Revised central force potentials for water Stillinger, F. H.; Rahman, A. The Journal of Chemical Physics, Vol. 68, Issue 2 https://doi.org/10.1063/1.435738	journal	January 1978
Molecular dynamics with coupling to an external bath Berendsen, H. J. C.; Postma, J. P. M.; van Gunsteren, W. F. The Journal of Chemical Physics, Vol. 81, Issue 8 https://doi.org/10.1063/1.448118	journal	October 1984
Multiple d ‐type basis functions for molecules containing second row atoms Magnusson, Eric; Schaefer, Henry F. The Journal of Chemical Physics, Vol. 83, Issue 11 https://doi.org/10.1063/1.449647	journal	December 1985
Multiple-scattering calculations of x-ray-absorption spectra Zabinsky, S. I.; Rehr, J. J.; Ankudinov, A. Physical Review B, Vol. 52, Issue 4 https://doi.org/10.1103/PhysRevB.52.2995	journal	July 1995
Tensor X-ray optical properties of the bromate ion Templeton, D. H.; Templeton, L. K. Acta Crystallographica Section A Foundations of Crystallography, Vol. 41, Issue 2 https://doi.org/10.1107/S0108767385000277	journal	March 1985
The Cambridge Structural Database: a quarter of a million crystal structures and rising Allen, Frank H. Acta Crystallographica Section B Structural Science, Vol. 58, Issue 3 https://doi.org/10.1107/S0108768102003890	journal	May 2002
Remeasurement of optically active NaClO ₃ and NaBrO ₃ Abrahams, S. C.; Bernstein, J. L. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 33, Issue 11 https://doi.org/10.1107/S0567740877011637	journal	November 1977
Hydrated metal ions in aqueous solution: How regular are their structures? Persson, Ingmar Pure and Applied Chemistry, Vol. 82, Issue 10 https://doi.org/10.1351/PAC-CON-09-10-22	journal	August 2010
Kinetics and Regulation of the NAD(P)H-Dependent Glyoxylate-Specific Reductase from Spinach Leaves Kleczkowski, Leszek A. Zeitschrift für Naturforschung C, Vol. 50, Issue 1-2 https://doi.org/10.1515/znc-1995-1-205	journal	February 1995

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