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

Wang, Hsiu-Wen; Vlcek, Lukas; Neuefeind, Joerg C.; Page, Katharine L.; Irle, Stephan; Simonson, J. Michael; Stack, Andrew G.

doi:10.1021/acs.jpcb.8b05895

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

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Abstract

We present that 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. Finally, this insight demonstrates the utility of experimental diffraction data for benchmarking atomistic computer simulations, enabling the development of more accurate intermolecular potentials.

Authors:

^[1];

^[2];

^[3]; Simonson, J. Michael ^[2];

^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Computational Sciences & Engineering Division

Publication Date:: Tue Jul 10 00:00:00 EDT 2018

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

OSTI Identifier:: 1474588

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

Additional Journal Information:: Journal Volume: 122; Journal Issue: 30; Journal ID: ISSN 1520-6106

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Wang, Hsiu-Wen, Vlcek, Lukas, Neuefeind, Joerg C., Page, Katharine L., Irle, Stephan, Simonson, J. Michael, and Stack, Andrew G. Decoding Oxyanion Aqueous Solvation Structure: A Potassium Nitrate Example at Saturation.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.jpcb.8b05895.

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                    Wang, Hsiu-Wen, Vlcek, Lukas, Neuefeind, Joerg C., Page, Katharine L., Irle, Stephan, Simonson, J. Michael, & Stack, Andrew G. Decoding Oxyanion Aqueous Solvation Structure: A Potassium Nitrate Example at Saturation.  United States.  https://doi.org/10.1021/acs.jpcb.8b05895

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                    Wang, Hsiu-Wen, Vlcek, Lukas, Neuefeind, Joerg C., Page, Katharine L., Irle, Stephan, Simonson, J. Michael, and Stack, Andrew G. Tue .  
"Decoding Oxyanion Aqueous Solvation Structure: A Potassium Nitrate Example at Saturation".  United States.  https://doi.org/10.1021/acs.jpcb.8b05895.  https://www.osti.gov/servlets/purl/1474588.

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@article{osti_1474588,

  title        = {Decoding Oxyanion Aqueous Solvation Structure: A Potassium Nitrate Example at Saturation},

  author       = {Wang, Hsiu-Wen and Vlcek, Lukas and Neuefeind, Joerg C. and Page, Katharine L. and Irle, Stephan and Simonson, J. Michael and Stack, Andrew G.},

  abstractNote = {We present that 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. Finally, this insight demonstrates the utility of experimental diffraction data for benchmarking atomistic computer simulations, enabling the development of more accurate intermolecular potentials.},

  doi          = {10.1021/acs.jpcb.8b05895},

  journal      = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},

  number       = 30,

  volume       = 122,

  place        = {United States},

  year         = {Tue Jul 10 00:00:00 EDT 2018},

  month        = {Tue Jul 10 00:00:00 EDT 2018}

}

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