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Title: Understanding the Scale of the Single Ion Free Energy: A Critical Test of the Tetra-Phenyl Arsonium and Tetra-Phenyl Borate Assumption

Abstract

Free energies, enthalpies and entropies of ions in solution can be experimentally determined for neutral pairs. For individual ions however, determining these properties requires additional assumptions, which can and should be theoretically tested. The tetra-phenyl arsonium and tetra-phenyl borate (TATB) assumption is a commonly used extra-thermodynamic assumption, which allows these values to be split into cationic and anionic contributions. The assumption is that the values for the TATB salt can be divided equally. This is justified by arguing that these large hydrophobic ions will cause a symmetric response in water. Experimental and classical simulation work has raised potential flaws with this assumption, indicating that hydrogen bonding with the phenyl ring may favor the solvation of the TB-anion. In this study, we perform ab initio molecular dynamics (AIMD) simulations of these ions in bulk water demonstrating that there are significant structural differences. We quantify our findings by reproducing the experimentally observed vibrational shift for the TB-anion and confirm that this is associated with hydrogen bonding with the phenyl rings. Finally, we demonstrate that this results in a substantial energetic preference of the water to solvate the anion. In conclusion, our results suggest that the validity of the TATB assumption, which ismore » still widely used today, should be reconsidered experimentally in order to properly reference single ion solvation free energy, enthalpy and entropy.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]
+ Show Author Affiliations
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Univ. of Queensland, Brisbane (Australia)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States) ; Univ. of Washington, Seattle, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1492309
Alternate Identifier(s):
OSTI ID: 1429143
Report Number(s):
PNNL-SA-132440
Journal ID: ISSN 0021-9606
Grant/Contract Number:  
AC05-76RL01830; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 22; 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; ab initio MD; rst principles MD; electrolyte; ions; solvation free energies

Citation Formats

Duignan, Timothy T., Baer, Marcel D., and Mundy, Christopher J. Understanding the Scale of the Single Ion Free Energy: A Critical Test of the Tetra-Phenyl Arsonium and Tetra-Phenyl Borate Assumption. United States: N. p., 2018. Web. doi:10.1063/1.5020171.
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Duignan, Timothy T., Baer, Marcel D., & Mundy, Christopher J. Understanding the Scale of the Single Ion Free Energy: A Critical Test of the Tetra-Phenyl Arsonium and Tetra-Phenyl Borate Assumption. United States. https://doi.org/10.1063/1.5020171
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Duignan, Timothy T., Baer, Marcel D., and Mundy, Christopher J. Fri . "Understanding the Scale of the Single Ion Free Energy: A Critical Test of the Tetra-Phenyl Arsonium and Tetra-Phenyl Borate Assumption". United States. https://doi.org/10.1063/1.5020171. https://www.osti.gov/servlets/purl/1492309.
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@article{osti_1492309,
title = {Understanding the Scale of the Single Ion Free Energy: A Critical Test of the Tetra-Phenyl Arsonium and Tetra-Phenyl Borate Assumption},
author = {Duignan, Timothy T. and Baer, Marcel D. and Mundy, Christopher J.},
abstractNote = {Free energies, enthalpies and entropies of ions in solution can be experimentally determined for neutral pairs. For individual ions however, determining these properties requires additional assumptions, which can and should be theoretically tested. The tetra-phenyl arsonium and tetra-phenyl borate (TATB) assumption is a commonly used extra-thermodynamic assumption, which allows these values to be split into cationic and anionic contributions. The assumption is that the values for the TATB salt can be divided equally. This is justified by arguing that these large hydrophobic ions will cause a symmetric response in water. Experimental and classical simulation work has raised potential flaws with this assumption, indicating that hydrogen bonding with the phenyl ring may favor the solvation of the TB-anion. In this study, we perform ab initio molecular dynamics (AIMD) simulations of these ions in bulk water demonstrating that there are significant structural differences. We quantify our findings by reproducing the experimentally observed vibrational shift for the TB-anion and confirm that this is associated with hydrogen bonding with the phenyl rings. Finally, we demonstrate that this results in a substantial energetic preference of the water to solvate the anion. In conclusion, our results suggest that the validity of the TATB assumption, which is still widely used today, should be reconsidered experimentally in order to properly reference single ion solvation free energy, enthalpy and entropy.},
doi = {10.1063/1.5020171},
journal = {Journal of Chemical Physics},
number = 22,
volume = 148,
place = {United States},
year = {Fri Mar 23 00:00:00 EDT 2018},
month = {Fri Mar 23 00:00:00 EDT 2018}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1063/1.5020171
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Cited by: 16 works
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Figures / Tables:

FIG. 1. FIG. 1. : Solvation free energies of the alkali halide ions with the CPA approximation in comparison to the TATB approximation.
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