Effects of applied voltage on water at a gold electrode interface from <i>ab initio</i> molecular dynamics

Goldsmith, Zachary K.; Andrade, Mauro; Selloni, Annabella

doi:10.1039/d1sc00354b

Cited by 43 publications

(43 citation statements)

References 79 publications

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“…Structural changes were observed in the solvent layers at the interface; these were particularly significant when σ was large, in line with simulations elsewhere studying electrified planar interfaces. 89 Fig. S18 † shows that when σ was large and positive, water oxygen atoms were pulled closer to the surface and peaks in n Hw ( x ) appear sharper.…”

Section: Resultsmentioning

confidence: 99%

Electrochemistry, ion adsorption and dynamics in the double layer: a study of NaCl(aq) on graphite

et al. 2021

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Section: Resultsmentioning

confidence: 99%

Electrochemistry, ion adsorption and dynamics in the double layer: a study of NaCl(aq) on graphite

et al. 2021

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“…From this perspective, the actual developments of first-principles machine-learned interatomic potentials are probably most exciting. 81,82 Explicit AIMD data 43,44,56,58,66,68,69,335,368,369,[459][460][461][462][463][464] has long been used to validate and improve implicit solvation methodology. If machine-learned interatomic potentials allow to generate comparably accurate, but orders of magnitude longer trajectories and in larger simulation cells, then this will be an invaluable asset that might even ultimately enable to validate and refine implicit solvation schemes for application outside the domain of ab initio thermodynamics, notably the modeling of kinetic reaction barriers.…”

Section: Discussionmentioning

confidence: 99%

Implicit Solvation Methods for Catalysis at Electrified Interfaces

Ringe¹,

Hörmann²,

Oberhofer³

et al. 2021

Preprint

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Implicit solvation is an effective, highly coarse-grained approach in atomic-scale simulations to account for a surrounding liquid electrolyte on the level of a continuous polarizable medium. Originating in molecular chemistry with finite solutes, implicit solvation techniques are now increasingly used in the context of first-principles modeling of electrochemistry and electrocatalysis at extended (often metallic) electrodes.The prevalent ansatz to model the latter electrodes and the reactive surface chemistry at them through slabs in periodic boundary condition supercells brings its specific challenges. Foremost this concerns the diffculty to describe the entire double layer forming at the electrified solid-liquid interface (SLI) within supercell sizes tractable

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“…This in turn lowers the continuum charging capacitance. [43] For instance, the capacitance is 14.3 mF/cm 2 with a ~15 Å liquid water film on a Au(111) surface [44] compared to values ranging from 18 to 30 mF/cm 2 without explicit water molecules depending on the continuum charging method. [10,45] Explicit charging of water-metal interfaces with cation-electron pairs do not suffer from the same capacitance problems, because the cations can move close to the metal surface.…”

Section: Explicit Charging In Relation To Other Constant Potential Ap...mentioning

confidence: 99%

Modeling electrochemical proton adsorption at constant potential with explicit charging

Kristoffersen

2022

Preprint

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I present an explicit charging approach to account for constant potential in atomic level electrochemistry modeling. Explicit charging allows us to calculate electrochemical reaction barriers, while also reproducing the results from the computation hydrogen electrode (CHE) approach when the reaction modeled with CHE is at constant potential. I use explicit charging to obtain activation and adsorption free energies for proton adsorption (the Volmer reaction) from a static water bilayer to the Cu(111) surface. Proton adsorption becomes spontaneous at around 0 V vs RHE and the adsorption free energy changes by around 1 eV per V (similar to the CHE result). The activation free energy changes by around 0.5 eV per V, but is still prohibitively large at 0 V vs RHE. This is consistent with experiments, where hydrogen evolution is only observed below -0.4 V vs RHE.

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Effects of applied voltage on water at a gold electrode interface from ab initio molecular dynamics

Abstract: Electrode-water interfaces under voltage bias demonstrate anomalous electrostatic and structural properties that are influential in their catalytic and technological applications. Mean-field and empirical models of the electrical double layer (EDL)...

Cited by 43 publications

References 79 publications

Electrochemistry, ion adsorption and dynamics in the double layer: a study of NaCl(aq) on graphite

Electrochemistry, ion adsorption and dynamics in the double layer: a study of NaCl(aq) on graphite

Implicit Solvation Methods for Catalysis at Electrified Interfaces

Modeling electrochemical proton adsorption at constant potential with explicit charging

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