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Title: Challenges in Modeling Electrochemical Reaction Energetics with Polarizable Continuum Models

Abstract

A major challenge in the modeling of electrochemical phenomena is the accurate description of the interface between an electrolyte and a charged conductor. Polarizable continuum models (PCM) have been gaining popularity because they offer a computationally inexpensive method of modeling the electrolyte. In this Perspective, we discuss challenges from using one such model which treats the ions using a linearized Poisson-Boltzmann (LPB) distribution. From a physical perspective, this model places charge unphysically close to the surface and adsorbates, and it includes excessively steep ramping of the dielectric constant from the surface to the bulk solvent. Both of these issues can be somewhat mitigated by adjusting parameters built into the model, but in doing so, the resultant capacitance deviates from experimental values. Likewise, hybrid explicit-implicit approaches to the solvent may offer a more realistic description of hydrogen bonding and solvation to reaction intermediates, but the corresponding capacitances also deviate from experimental values. These deviations highlight the need for a careful adjustment of parameters in order to reproduce not only solvation energies but also other physical properties of solid-liquid interfaces. Continuum approaches alone also necessarily do not capture local variations in the electric field from cations at the interface, which can affectmore » the energetics of intermediates with substantial dipoles or polarizability. Finally, since the double-layer charge can be varied continuously, LPB/PCM models provide a way to determine electrochemical barriers at constant potential. However, double-layer charging and the atomic motion associated with reaction events occur on significantly different timescales. We suggest that more detailed approaches, such as the modified Poisson-Boltzmann model and/or the addition of a Stern layer, may be able to mitigate some but not all of the challenges discussed.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1];  [3]; ORCiD logo [4]; ORCiD logo [4];  [1]; ORCiD logo [5]
+ Show Author Affiliations
  1. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1507029
Alternate Identifier(s):
OSTI ID: 1542366
Grant/Contract Number:  
AC02-76SF00515; DGE-114747; SC00004993; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 9; Journal Issue: 2; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis; density functional theory; electrocatalysis; electrochemistry; solvation

Citation Formats

Gauthier, Joseph A., Ringe, Stefan, Dickens, Colin F., Garza, Alejandro J., Bell, Alexis T., Head-Gordon, Martin, Nørskov, Jens K., and Chan, Karen. Challenges in Modeling Electrochemical Reaction Energetics with Polarizable Continuum Models. United States: N. p., 2018. Web. doi:10.1021/acscatal.8b02793.
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Gauthier, Joseph A., Ringe, Stefan, Dickens, Colin F., Garza, Alejandro J., Bell, Alexis T., Head-Gordon, Martin, Nørskov, Jens K., & Chan, Karen. Challenges in Modeling Electrochemical Reaction Energetics with Polarizable Continuum Models. United States. https://doi.org/10.1021/acscatal.8b02793
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Gauthier, Joseph A., Ringe, Stefan, Dickens, Colin F., Garza, Alejandro J., Bell, Alexis T., Head-Gordon, Martin, Nørskov, Jens K., and Chan, Karen. Wed . "Challenges in Modeling Electrochemical Reaction Energetics with Polarizable Continuum Models". United States. https://doi.org/10.1021/acscatal.8b02793. https://www.osti.gov/servlets/purl/1507029.
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@article{osti_1507029,
title = {Challenges in Modeling Electrochemical Reaction Energetics with Polarizable Continuum Models},
author = {Gauthier, Joseph A. and Ringe, Stefan and Dickens, Colin F. and Garza, Alejandro J. and Bell, Alexis T. and Head-Gordon, Martin and Nørskov, Jens K. and Chan, Karen},
abstractNote = {A major challenge in the modeling of electrochemical phenomena is the accurate description of the interface between an electrolyte and a charged conductor. Polarizable continuum models (PCM) have been gaining popularity because they offer a computationally inexpensive method of modeling the electrolyte. In this Perspective, we discuss challenges from using one such model which treats the ions using a linearized Poisson-Boltzmann (LPB) distribution. From a physical perspective, this model places charge unphysically close to the surface and adsorbates, and it includes excessively steep ramping of the dielectric constant from the surface to the bulk solvent. Both of these issues can be somewhat mitigated by adjusting parameters built into the model, but in doing so, the resultant capacitance deviates from experimental values. Likewise, hybrid explicit-implicit approaches to the solvent may offer a more realistic description of hydrogen bonding and solvation to reaction intermediates, but the corresponding capacitances also deviate from experimental values. These deviations highlight the need for a careful adjustment of parameters in order to reproduce not only solvation energies but also other physical properties of solid-liquid interfaces. Continuum approaches alone also necessarily do not capture local variations in the electric field from cations at the interface, which can affect the energetics of intermediates with substantial dipoles or polarizability. Finally, since the double-layer charge can be varied continuously, LPB/PCM models provide a way to determine electrochemical barriers at constant potential. However, double-layer charging and the atomic motion associated with reaction events occur on significantly different timescales. We suggest that more detailed approaches, such as the modified Poisson-Boltzmann model and/or the addition of a Stern layer, may be able to mitigate some but not all of the challenges discussed.},
doi = {10.1021/acscatal.8b02793},
journal = {ACS Catalysis},
number = 2,
volume = 9,
place = {United States},
year = {Wed Nov 28 00:00:00 EST 2018},
month = {Wed Nov 28 00:00:00 EST 2018}
}
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Quantum-continuum simulation of the electrochemical response of pseudocapacitor electrodes under realistic conditions
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Simple Marcus-Theory-Type Model for Hydrogen-Atom Transfer/Proton-Coupled Electron Transfer
journal, May 2011

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  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 23
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The Potential of Zero Charge
book, January 2002

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