Controlling electrochemical reactivity requires a detailed understanding of the charging behavior and thermodynamics of the electrochemical interface. Experiments can independently probe the overall charge response of the electrochemical double layer by capacitance measurements and the thermodynamics of the inner layer with potential of maximum entropy measurements. Relating these properties by computational modeling of the electrochemical interface has so far been challenging due to the low accuracy of classical molecular dynamics (MD) for capacitance and the limited time and length scales of ab initio MD. Here, we combine large ensembles of long-time-scale classical MD simulations with charge response from electronic density functional theory to predict the potential-dependent capacitance of a family of ideal aqueous electrochemical interfaces with different peak capacitances. We show that while the potential of maximum capacitance varies, this entire family exhibits an electrode charge of maximum capacitance (CMC) between −2.9 and −2.2 μC/cm2, regardless of the details in the electronic response. Simulated heating of the same interfaces reveals that the entropy peaks at a charge of maximum entropy (CME) of −5.1 ± 0.6 μC/cm2, in agreement with experimental findings for metallic electrodes. The CME and CMC both indicate asymmetric response of interfacial water that is stronger for negatively charged electrodes, while the difference between CME and CMC illustrates the richness in behavior of even the ideal electrochemical interface.
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7 January 2022
Research Article|
January 06 2022
Interfacial water asymmetry at ideal electrochemical interfaces
Special Collection:
The Chemical Physics of the Electrode-Electrolyte Interface
Abhishek Shandilya
;
Abhishek Shandilya
1
Department of Materials Science and Engineering, Rensselaer Polytechnic Institute
, Troy, New York 12180, USA
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Kathleen Schwarz
;
Kathleen Schwarz
a)
2
Material Measurement Laboratory, National Institute of Standards and Technology
, Gaithersburg, Maryland 20899, USA
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Ravishankar Sundararaman
Ravishankar Sundararaman
b)
1
Department of Materials Science and Engineering, Rensselaer Polytechnic Institute
, Troy, New York 12180, USA
b)Author to whom correspondence should be addressed: [email protected]
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a)
Electronic mail: [email protected]
b)Author to whom correspondence should be addressed: [email protected]
Note: This paper is part of the JCP Special Topic on The Chemical Physics of the Electrode–Electrolyte Interface.
J. Chem. Phys. 156, 014705 (2022)
Article history
Received:
October 20 2021
Accepted:
December 14 2021
Citation
Abhishek Shandilya, Kathleen Schwarz, Ravishankar Sundararaman; Interfacial water asymmetry at ideal electrochemical interfaces. J. Chem. Phys. 7 January 2022; 156 (1): 014705. https://doi.org/10.1063/5.0076038
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Erratum: “Interfacial water asymmetry at ideal electrochemical interfaces” [J. Chem. Phys. 156, 014705 (2022)]
J. Chem. Phys. (March 2022)