Hydrogen and Higher Shell Contributions in Zn2+, Ni2+, and Co2+ Aqueous Solutions:  An X-ray Absorption Fine Structure and Molecular Dynamics Study

D’Angelo, P.; Barone, Vincenzo; Chillemi, Giovanni; Sanna, Nico; Meyer‐Klaucke, Wolfram; Pavel, Nicolae Viorel

doi:10.1021/ja015685x

Cited by 181 publications

(230 citation statements)

References 41 publications

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“…Other authors, who do not use the same methodological approach to compute the EXAFS spectra, work with the assumption of using hydrogen atoms as backscatterers in both anion and cation studies. 17 The different strategy handling cation and anion hydration, apart from its heuristical justification as seen in Figs. 3 and 4, could be understood by the presence of a closest hydrogen shell around the anion.…”

Section: Methodsmentioning

confidence: 99%

“…This procedure has proven to be successful in many studies of structural elucidation of solid and liquid systems. [12][13][14][15][16][17] The aim of this work is to obtain the bromide hydration structure by means of the combination of experimental information derived from XAS techniques and theoretical data from computer simulations. When dealing with the structural description of ionic solutions, the patterns for the cation and anion hydration are far from similar, mostly due to two reasons.…”

Section: Introductionmentioning

confidence: 99%

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Interplay of computer simulations and x-ray absorption spectra in the study of the bromide hydration structure

Merkling

Ayala

Martı́nez

et al. 2003

The Journal of Chemical Physics

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X-ray absorption spectra EXAFS and XANES were generated from snapshots of a Monte Carlo MC simulation of a bromide ion aqueous solution and from model structures. The MC simulation relies on a recently developed and tested polarizable potential based on ab initio potential energy surfaces. A comparison with the experimental K-edge Br spectrum of a 0.3 M YBr 3 aqueous solution was performed. XANES spectra are reproduced acceptably only if statistical fluctuations are included, which is performed in this work by using snapshots from computer simulation. As expected, single scattering BrO contributions are dominant in the case of the EXAFS region. Due to this fact, Br in water is a good model system for studying the influence of the distribution of distances on the determination of structural parameters. Then, a parallel study of the data analysis procedure of the experimental EXAFS spectrum and those theoretically computed from the structures supplied by the MC simulation, was carried out. The shape of the distribution function and its asymmetry must be taken into account in a practical way to obtain a more accurate determination of the BrO first-shell distance. A further refinement consists in using the computer simulation to extrapolate the BrO distance from the experimental EXAFS spectrum. In this way, a BrO distance of 3.44 0.07 Å and a coordination number of 6 0.5 were determined.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Interplay of computer simulations and x-ray absorption spectra in the study of the bromide hydration structure

Merkling

Ayala

Martı́nez

et al. 2003

The Journal of Chemical Physics

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“…Such simulations can be an important adjunct to spectroscopic measurements of speciation and can explore PT regimes not accessible via experiment. Several groups have combined MD and EXAFS spectroscopy to study the stoichiometry and geometry of aqueous metal complexes (e.g., D'Angelo et al, 2002;Dang et al, 2006;Fulton et al, 2009;Hoffmann et al, 1999).…”

Section: Molecular Understanding Of Metal Transport In Hydrothermal Fmentioning

confidence: 99%

Ab initio molecular dynamics simulation and free energy exploration of copper(I) complexation by chloride and bisulfide in hydrothermal fluids

Mei

Sherman

Liu

et al. 2013

Geochimica et Cosmochimica Acta

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Ab initio molecular dynamics simulation and free energy exploration of copper(I) complexation by chloride and bisulfide in hydrothermal fluids Geochimica et Cosmochimica Acta, 2013; 102:45-64 © 2012 Elsevier Ltd. All rights reserved. NOTICE: this is the author's version of a work that was accepted for publication in Geochimica et Cosmochimica Acta. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Geochimica et Cosmochimica Acta, 2013; 102:45-64 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.Ab initio MD simulation of Cu(I) complexation

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“…45,54,[56][57][58][59] However, we also compared the x-ray scattering calculated from the simulated structures directly to the observed EXAFS spectra. 36 This type of analysis has recently been used to compare AIMD simulations of UO 2 2+ + 64H 2 O ͑UO 2 2+ + 122H 2 O͒ to EXAFS measurements with remarkable success.…”

Section: B Comparison Of Simulations With Exafs Datamentioning

confidence: 99%

Structure and dynamics of the hydration shells of the Zn2+ ion from ab initio molecular dynamics and combined ab initio and classical molecular dynamics simulations

Cauët

Bogatko

Weare

et al. 2010

The Journal of Chemical Physics

102

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Results of ab initio molecular dynamics ͑AIMD͒ simulations ͑density functional theory+ PBE96͒ of the dynamics of waters in the hydration shells surrounding the Zn 2+ ion ͑T Ϸ 300 K, Ϸ 1 gm/ cm 3 ͒ are compared to simulations using a combined quantum and classical molecular dynamics ͓AIMD/molecular mechanical ͑MM͔͒ approach. Both classes of simulations were performed with 64 solvating water molecules ͑ϳ15 ps͒ and used the same methods in the electronic structure calculation ͑plane-wave basis set, time steps, effective mass, etc.͒. In the AIMD/MM calculation, only six waters of hydration were included in the quantum mechanical ͑QM͒ region. The remaining 58 waters were treated with a published flexible water-water interaction potential. No reparametrization of the water-water potential was attempted. Additional AIMD/MM simulations were performed with 256 water molecules. The hydration structures predicted from the AIMD and AIMD/MM simulations are found to agree in detail with each other and with the structural results from x-ray data despite the very limited QM region in the AIMD/MM simulation. To further evaluate the agreement of these parameter-free simulations, predicted extended x-ray absorption fine structure ͑EXAFS͒ spectra were compared directly to the recently obtained EXAFS data and they agree in remarkable detail with the experimental observations. The first hydration shell contains six water molecules in a highly symmetric octahedral structure is ͑maximally located at 2.13-2.15 Å versus 2.072 Å EXAFS experiment͒. The widths of the peak of the simulated EXAFS spectra agree well with the data ͑8.4 Å 2 versus 8.9 Å 2 in experiment͒. Analysis of the H-bond structure of the hydration region shows that the second hydration shell is trigonally bound to the first shell water with a high degree of agreement between the AIMD and AIMD/MM calculations. Beyond the second shell, the bonding pattern returns to the tetrahedral structure of bulk water. The AIMD/MM results emphasize the importance of a quantum description of the first hydration shell to correctly describe the hydration region. In these calculations the full d 10 electronic structure of the valence shell of the Zn 2+ ion is retained. The simulations show substantial and complex charge relocation on both the Zn 2+ ion and the first hydration shell. The dipole moment of the waters in the first hydration shell is 3.4 D ͑3.3 D AIMD/MM͒ versus 2.73 D bulk. Little polarization is found for the waters in the second hydration shell ͑2.8 D͒. No exchanges were seen between the first and the second hydrations shells; however, many water transfers between the second hydration shell and the bulk were observed. For 64 waters, the AIMD and AIMD/MM simulations give nearly identical results for exchange dynamics. However, in the larger particle simulations ͑256 waters͒ there is a significant reduction in the second shell to bulk exchanges.

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Hydrogen and Higher Shell Contributions in Zn²⁺, Ni²⁺, and Co²⁺ Aqueous Solutions: An X-ray Absorption Fine Structure and Molecular Dynamics Study

Cited by 181 publications

References 41 publications

Interplay of computer simulations and x-ray absorption spectra in the study of the bromide hydration structure

Interplay of computer simulations and x-ray absorption spectra in the study of the bromide hydration structure

Ab initio molecular dynamics simulation and free energy exploration of copper(I) complexation by chloride and bisulfide in hydrothermal fluids

Structure and dynamics of the hydration shells of the Zn2+ ion from ab initio molecular dynamics and combined ab initio and classical molecular dynamics simulations

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