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Decoding Oxyanion Aqueous Solvation Structure: A Potassium Nitrate Example at Saturation

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    Decoding Oxyanion Aqueous Solvation Structure: A Potassium Nitrate Example at Saturation
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    The Journal of Physical Chemistry B

    Cite this: J. Phys. Chem. B 2018, 122, 30, 7584–7589
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    https://doi.org/10.1021/acs.jpcb.8b05895
    Published July 10, 2018
    Copyright © 2018 American Chemical Society
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    Abstract

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    The ability to probe the structure of a salt solution at the atomic scale is fundamentally important for our understanding of many chemical reactions and their mechanisms. The capability of neutron diffraction to “see” hydrogen (or deuterium) and other light isotopes is exceptional for resolving the structural complexity around the dissolved solutes in aqueous electrolytes. We have made measurements using oxygen isotopes on aqueous nitrate to reveal a small hydrogen-bonded water coordination number (3.9 ± 1.2) around a nitrate oxyanion. This is compared to estimates made using the existing method of nitrogen isotope substitution and those of computational simulations (>5–6 water molecules). The low water coordination number, combined with a comparison to classical molecular dynamics simulations, suggests that ion-pair formation is significant. This insight demonstrates the utility of experimental diffraction data for benchmarking atomistic computer simulations, enabling the development of more accurate intermolecular potentials.

    Copyright © 2018 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcb.8b05895.

    • Section 1: Discussions of solution preparation, composition and number density including a table of the stoichiometric composition. Section 2: Eequations on NDIS and first-order difference approaches with a table giving the numbers of water and K cations around one nitrate ion. Section 3: NDIS data reduction with related figures. Section 4: Comparison of N-NDIS data to the published work. Section 5: Optimization of force field parameters with a figure of contributions of the five relevant RDFs to the normalized experimental RDF. Section 6: A brief summary of NO3– hydration by MD simulations. Section 7: Concentration error analysis and related figures (PDF)

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    The Journal of Physical Chemistry B

    Cite this: J. Phys. Chem. B 2018, 122, 30, 7584–7589
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpcb.8b05895
    Published July 10, 2018
    Copyright © 2018 American Chemical Society
    Request reuse permissions

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