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Title: Exploring chemical speciation at electrified interfaces using detailed continuum models

Abstract

We present a local free-energy functional-based generic continuum model for material interfaces with a specific emphasis on electrified solid/liquid interfaces. The model enables a description of multicomponent phases at interfaces and includes the effects of specific non-electrostatic interactions (specific adsorption), ion size disparity, and the explicit presence of neutral species. In addition to the optimization of electrostatic, non-electrostatic, and steric forces, the model can be easily modified to explore the effects of other channels for equilibration, including local chemical transformations driven by equilibrium constants and electrochemical reactions driven by the electrode potential. In this way, we show that, upon accounting for these effects, local speciation in the vicinity of the interface can be drastically different from what is expected from restricted models and minor species (from the bulk perspective) may become dominant due to the effects of local pH. We evaluate the ionic contribution to the surface tension at the interface and show how this could impact the structure of air/liquid interfaces. On the same footing, an attempt to describe electrochemical metal dissolution is made. The model allows estimates of the mutual population of newly produced ions depending on their charge and size and could be useful for interpretation ofmore » electrochemical and spectroscopic measurements if the dissolution involves different metal ions (species). With these advances, the proposed model may be used as an ingredient within a hybrid ab initio-continuum methodology to model biased interfaces.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]
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  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). The Joint Center for Energy Storage Research, The Molecular Foundry
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1543894
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 4; 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; Chemistry; Physics

Citation Formats

Baskin, Artem, and Prendergast, David. Exploring chemical speciation at electrified interfaces using detailed continuum models. United States: N. p., 2019. Web. doi:10.1063/1.5058159.
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Baskin, Artem, & Prendergast, David. Exploring chemical speciation at electrified interfaces using detailed continuum models. United States. https://doi.org/10.1063/1.5058159
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Baskin, Artem, and Prendergast, David. Fri . "Exploring chemical speciation at electrified interfaces using detailed continuum models". United States. https://doi.org/10.1063/1.5058159. https://www.osti.gov/servlets/purl/1543894.
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@article{osti_1543894,
title = {Exploring chemical speciation at electrified interfaces using detailed continuum models},
author = {Baskin, Artem and Prendergast, David},
abstractNote = {We present a local free-energy functional-based generic continuum model for material interfaces with a specific emphasis on electrified solid/liquid interfaces. The model enables a description of multicomponent phases at interfaces and includes the effects of specific non-electrostatic interactions (specific adsorption), ion size disparity, and the explicit presence of neutral species. In addition to the optimization of electrostatic, non-electrostatic, and steric forces, the model can be easily modified to explore the effects of other channels for equilibration, including local chemical transformations driven by equilibrium constants and electrochemical reactions driven by the electrode potential. In this way, we show that, upon accounting for these effects, local speciation in the vicinity of the interface can be drastically different from what is expected from restricted models and minor species (from the bulk perspective) may become dominant due to the effects of local pH. We evaluate the ionic contribution to the surface tension at the interface and show how this could impact the structure of air/liquid interfaces. On the same footing, an attempt to describe electrochemical metal dissolution is made. The model allows estimates of the mutual population of newly produced ions depending on their charge and size and could be useful for interpretation of electrochemical and spectroscopic measurements if the dissolution involves different metal ions (species). With these advances, the proposed model may be used as an ingredient within a hybrid ab initio-continuum methodology to model biased interfaces.},
doi = {10.1063/1.5058159},
journal = {Journal of Chemical Physics},
number = 4,
volume = 150,
place = {United States},
year = {2019},
month = {1}
}
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Journal Article:
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https://doi.org/10.1063/1.5058159
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Figures / Tables:

FIG. 1 FIG. 1: Self-consistent computational scheme of evaluation of density profiles of three ions when chemical equilibration is accounted for on top of the relaxation of electrostatic and entropic forces. MPBE stands for the modified Poisson-Boltzmann equation. Conditions of each step of calculation are indicated inside each block. Captions for eachmore » arrow indicate the output of calculations at the previous step.« less
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    Special Topic on Interfacial Electrochemistry and Photo(electro)catalysis
    journal, January 2019

    • Lian, Tianquan; Koper, Marc T. M.; Reuter, Karsten
    • The Journal of Chemical Physics, Vol. 150, Issue 4
    • DOI: 10.1063/1.5088351
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