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Many-Body Effects Determine the Local Hydration Structure of Cs+ in Solution
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    Many-Body Effects Determine the Local Hydration Structure of Cs+ in Solution
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    • Debbie Zhuang
      Debbie Zhuang
      Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, United States
    • Marc Riera
      Marc Riera
      Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, United States
      More by Marc Riera
    • Gregory K. Schenter
      Gregory K. Schenter
      Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
    • John L. Fulton*
      John L. Fulton
      Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
      *E-mail: [email protected]
    • Francesco Paesani*
      Francesco Paesani
      Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, United States
      Materials Science and Engineering, University of California, San Diego, La Jolla, California 92093, United States
      San Diego Supercomputer Center, University of California, San Diego, La Jolla, California 92093, United States
      *E-mail: [email protected]
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    The Journal of Physical Chemistry Letters

    Cite this: J. Phys. Chem. Lett. 2019, 10, 3, 406–412
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    https://doi.org/10.1021/acs.jpclett.8b03829
    Published January 10, 2019
    Copyright © 2019 American Chemical Society

    Abstract

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    A systematic analysis of the hydration structure of Cs+ ions in solution is derived from simulations carried out using a series of molecular models built upon a hierarchy of approximate representations of many-body effects in ion–water interactions. It is found that a pairwise-additive model, commonly used in biomolecular simulations, provides poor agreement with experimental X-ray spectra, indicating an incorrect description of the underlying hydration structure. Although the agreement with experiment improves in simulations with a polarizable model, the predicted hydration structure is found to lack the correct sequence of water shells. Progressive inclusion of explicit many-body effects in the representation of Cs+–water interactions as well as accounting for nuclear quantum effects is shown to be necessary for quantitatively reproducing the experimental X-ray spectra. Besides emphasizing the importance of many-body effects, these results suggest that molecular models rigorously derived from many-body expansions hold promise for realistic simulations of aqueous solutions.

    Copyright © 2019 American Chemical Society

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpclett.8b03829.

    • Computational details regarding both electronic structure calculations and molecular simulations. Experimental details regarding EXAFS measurements and processing, and sample preparation. Discussion of  multielectron absorption, concentration effects, and EXAFS calculations.  Model fits to experimental and theoretical EXAFS spectra, along with a table containing the structural parameters extracted from the EXAFS spectra. (PDF)

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    The Journal of Physical Chemistry Letters

    Cite this: J. Phys. Chem. Lett. 2019, 10, 3, 406–412
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpclett.8b03829
    Published January 10, 2019
    Copyright © 2019 American Chemical Society

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