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Title: Unraveling the Spectral Signatures of Solvent Ordering in K-edge XANES of Aqueous Na+

Abstract

The aqueous solvation structure of the Na+ ion is studied both by molecular dynamics (MD) simulations and K-edge X-ray absorption near edge spectroscopy (XANES). In this paper, we present a systematic study contrasting the differences in the predicted XANES spectra, using molecular configurations generated from classical and quantum MD. Using a set of suitable order parameters, we elucidate how the spectroscopic features are influenced by the local solvation structure around the Na+ ion. Lastly, our findings suggest that XANES is sensitive to fluctuations between the first and second solvation shells and can distinguish between classical and quantum interaction representations used to generate molecular ensembles.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1];  [1]
+ Show Author Affiliations
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States) ; Univ. of Washington, Seattle, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1492306
Alternate Identifier(s):
OSTI ID: 1472223
Report Number(s):
PNNL-SA-131808
Journal ID: ISSN 0021-9606
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 12; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Galib, M., Schenter, G. K., Mundy, C. J., Govind, N., and Fulton, J. L. Unraveling the Spectral Signatures of Solvent Ordering in K-edge XANES of Aqueous Na+. United States: N. p., 2018. Web. doi:10.1063/1.5024568.
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Galib, M., Schenter, G. K., Mundy, C. J., Govind, N., & Fulton, J. L. Unraveling the Spectral Signatures of Solvent Ordering in K-edge XANES of Aqueous Na+. United States. https://doi.org/10.1063/1.5024568
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Galib, M., Schenter, G. K., Mundy, C. J., Govind, N., and Fulton, J. L. Mon . "Unraveling the Spectral Signatures of Solvent Ordering in K-edge XANES of Aqueous Na+". United States. https://doi.org/10.1063/1.5024568. https://www.osti.gov/servlets/purl/1492306.
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@article{osti_1492306,
title = {Unraveling the Spectral Signatures of Solvent Ordering in K-edge XANES of Aqueous Na+},
author = {Galib, M. and Schenter, G. K. and Mundy, C. J. and Govind, N. and Fulton, J. L.},
abstractNote = {The aqueous solvation structure of the Na+ ion is studied both by molecular dynamics (MD) simulations and K-edge X-ray absorption near edge spectroscopy (XANES). In this paper, we present a systematic study contrasting the differences in the predicted XANES spectra, using molecular configurations generated from classical and quantum MD. Using a set of suitable order parameters, we elucidate how the spectroscopic features are influenced by the local solvation structure around the Na+ ion. Lastly, our findings suggest that XANES is sensitive to fluctuations between the first and second solvation shells and can distinguish between classical and quantum interaction representations used to generate molecular ensembles.},
doi = {10.1063/1.5024568},
journal = {Journal of Chemical Physics},
number = 12,
volume = 149,
place = {United States},
year = {2018},
month = {9}
}
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Journal Article:
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https://doi.org/10.1063/1.5024568
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Figures / Tables:

FIG. 1 FIG. 1: . Schematic representations of the order parameters as described in the main text. (a) The coordination number is defined as the number of water molecules in the first solvation shell. A large O–O distance deviation between two adjacent nearest neighbors defines the position between the first and secondmore » solvation shells. The water molecules in the gray area correspond to the first solvation shell and those in the blue area correspond to the second solvation shell. Both shells are clearly separated from each other as shown by the white area. (b) The INT6 order parameter distinguishes between an ordered and a disordered inter-shell structure. When INT6 >> 0, the second solvation shell is clearly separated from the first solvation shell. When INT6 = 0, an interstitial water resides between these two solvation shells. The fluctuation of the interstitial water diminishes the separated area between two solvation shells. (c) The tilt angle is defined as the angle between the vector from the oxygen to the ion and the dipole moment vector of the water molecule.« less
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    Works referencing / citing this record:

    Quantifying the hydration structure of sodium and potassium ions: taking additional steps on Jacob's Ladder
    journal, January 2020

    • Duignan, Timothy T.; Schenter, Gregory K.; Fulton, John L.
    • Physical Chemistry Chemical Physics
    • DOI: 10.1039/c9cp06161d

    Quantifying the hydration structure of sodium and potassium ions: taking additional steps on Jacob's Ladder
    text, January 2020

    • Duignan, Timothy T.; Schenter, Gregory K.; Fulton, John L.
    • Universität Regensburg
    • DOI: 10.5283/epub.45957
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