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Title: Water Lone Pair Delocalization in Classical and Quantum Descriptions of the Hydration of Model Ions

Abstract

Understanding the nature of ionic hydration at a fundamental level has eluded scientists despite intense interest for nearly a century. In particular, the microscopic origins of the asymmetry of ion solvation thermodynamics with respect to the sign of the ionic charge remains a mystery. Here, we determine the response of accurate quantum mechanical water models to strong nanoscale solvation forces arising from excluded volumes and ionic electrostatic fields. This is compared to the predictions of two important limiting classes of classical models of water with fixed point changes, differing in their treatment of “lone pair” electrons. Using the quantum water model as our standard of accuracy, we find that a single fixed classical treatment of lone pair electrons cannot accurately describe solvation of both apolar and cationic solutes, emphasizing the need for a more flexible description of local electronic effects in solvation processes. However, we explicitly show that all water models studied respond to weak long-ranged electrostatic perturbations in a manner that follows macroscopic dielectric continuum models, as would be expected. Here, we emphasize the importance of these findings in the context of realistic ion models, using density functional theory and empirical models, and discuss the implications of our resultsmore » for quantitatively accurate reduced descriptions of solvation in dielectric media.« less

Authors:
 [1]; ORCiD logo [2];  [2];  [2]; ORCiD logo [3]; ORCiD logo [4]
  1. Temple Univ., Philadelphia, PA (United States). Inst. for Computational Molecular Science
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Chemical and Materials Science Division
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Chemical and Materials Science Division; Univ. of Washington, Seattle, WA (United States). Dept. of Chemical Engineering
  4. Univ. of Maryland, College Park, MD (United States). Inst. for Physical Science and Technology and Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1480310
Grant/Contract Number:  
AC02-05CH11231
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: 13; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Remsing, Richard C., Duignan, Timothy T., Baer, Marcel D., Schenter, Gregory K., Mundy, Christopher J., and Weeks, John D.. Water Lone Pair Delocalization in Classical and Quantum Descriptions of the Hydration of Model Ions. United States: N. p., 2018. Web. https://doi.org/10.1021/acs.jpcb.7b10722.
Remsing, Richard C., Duignan, Timothy T., Baer, Marcel D., Schenter, Gregory K., Mundy, Christopher J., & Weeks, John D.. Water Lone Pair Delocalization in Classical and Quantum Descriptions of the Hydration of Model Ions. United States. https://doi.org/10.1021/acs.jpcb.7b10722
Remsing, Richard C., Duignan, Timothy T., Baer, Marcel D., Schenter, Gregory K., Mundy, Christopher J., and Weeks, John D.. Mon . "Water Lone Pair Delocalization in Classical and Quantum Descriptions of the Hydration of Model Ions". United States. https://doi.org/10.1021/acs.jpcb.7b10722. https://www.osti.gov/servlets/purl/1480310.
@article{osti_1480310,
title = {Water Lone Pair Delocalization in Classical and Quantum Descriptions of the Hydration of Model Ions},
author = {Remsing, Richard C. and Duignan, Timothy T. and Baer, Marcel D. and Schenter, Gregory K. and Mundy, Christopher J. and Weeks, John D.},
abstractNote = {Understanding the nature of ionic hydration at a fundamental level has eluded scientists despite intense interest for nearly a century. In particular, the microscopic origins of the asymmetry of ion solvation thermodynamics with respect to the sign of the ionic charge remains a mystery. Here, we determine the response of accurate quantum mechanical water models to strong nanoscale solvation forces arising from excluded volumes and ionic electrostatic fields. This is compared to the predictions of two important limiting classes of classical models of water with fixed point changes, differing in their treatment of “lone pair” electrons. Using the quantum water model as our standard of accuracy, we find that a single fixed classical treatment of lone pair electrons cannot accurately describe solvation of both apolar and cationic solutes, emphasizing the need for a more flexible description of local electronic effects in solvation processes. However, we explicitly show that all water models studied respond to weak long-ranged electrostatic perturbations in a manner that follows macroscopic dielectric continuum models, as would be expected. Here, we emphasize the importance of these findings in the context of realistic ion models, using density functional theory and empirical models, and discuss the implications of our results for quantitatively accurate reduced descriptions of solvation in dielectric media.},
doi = {10.1021/acs.jpcb.7b10722},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 13,
volume = 122,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
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Citation Metrics:
Cited by: 11 works
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Figures / Tables:

Figure 1 Figure 1: Matrix of probability distributions of water orientations in the first hydration shell of charged and uncharged hard spherical solutes with a radius of $R$HS = 2.6 Å. The top row is for SPC/E water, the middle row is for the revPBE-D3 DFT description of water, and the bottommore » row is for the TIP5P model of water. The left, center, and right columns correspond to hard sphere charges of $Q$ = -1, 0, and +1, respectively. Variations in the solid angle have been removed.« less

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