Continuum Embedding Models for Electrolyte Solutions in First‐Principles Simulations of Electrochemistry

Andreussi, Oliviero; Nattino, Francesco; Hörmann, Nicolas G.

doi:10.1002/9781119605652.ch3

Cited by 4 publications

(3 citation statements)

References 107 publications

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“…derivatives before and after adsorption in Figure S8 in the SI), hinting thus at another inherent accuracy limitation of implicit models. In addition, different models for the electrolyte might induce some variations of the interfacial capacitance with the potential, ,,, which can not be captured by construction in our model. Numerical experiments confirm though that these are not important for the studied halides.…”

Section: Discussionmentioning

confidence: 99%

Thermodynamic Cyclic Voltammograms Based onAb InitioCalculations: Ag(111) in Halide-Containing Solutions

Hörmann

2021

J. Chem. Theory Comput.

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Cyclic voltammograms (CVs) are a central experimental tool for assessing the structure and activity of electrochemical interfaces. Based on a mean-field ansatz for the interface energetics under applied potential conditions, we here derive an ab initio thermodynamics approach to efficiently simulate thermodynamic CVs. All unknown parameters are determined from density functional theory (DFT) calculations coupled to an implicit solvent model. For the showcased CVs of Ag(111) electrodes in halide-anion-containing solutions, these simulations demonstrate the relevance of double-layer contributions to explain experimentally observed differences in peak shapes over the halide series. Only the appropriate account of interfacial charging allows us to capture the differences in equilibrium coverage and total electronic surface charge that cause the varying peak shapes. As a case in point, this analysis demonstrates that prominent features in CVs do not only derive from changes in adsorbate structure or coverage but can also be related to variations of the electrosorption valency. Such double-layer effects are proportional to adsorbate-induced changes in the work function and/or interfacial capacitance. They are thus especially pronounced for electronegative halides and other adsorbates that affect these interface properties. In addition, the analysis allows us to draw conclusions on how the possible inaccuracy of implicit solvation models can indirectly affect the accuracy of other predicted quantities such as CVs.

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Section: Discussionmentioning

confidence: 99%

Thermodynamic Cyclic Voltammograms Based onAb InitioCalculations: Ag(111) in Halide-Containing Solutions

Hörmann

2021

J. Chem. Theory Comput.

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“…Constant-potential energetics can be derived from constant-charge calculations, which are generally easier to perform. ,− The most commonly used method is based on the second-order Taylor expansion of the energy series with respect to the charge q E ≈ E 0 + q ∂ E ∂ q true| q = 0 + 1 2 q 2 ∂ 2 E ∂ q 2 true| q = 0 where E 0 is the charge-neutral energy, the first derivative is the electrode potential with no surface charge (Φ 0 ), and the second derivative is the inverse of the capacitance C . This energy expression can be reorganized to be E = E 0 + C false( normalΦ − normalΦ 0 false) Φ 0 + C false( normalΦ − normalΦ 0 false) 2 2 where the capacitance can be obtained by calculating the potentials with different electron numbers .…”

Section: Methodsmentioning

confidence: 99%

Emerging Atomistic Modeling Methods for Heterogeneous Electrocatalysis

Levell,

Le,

et al. 2024

Chem. Rev.

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Heterogeneous electrocatalysis lies at the center of various technologies that could help enable a sustainable future. However, its complexity makes it challenging to accurately and efficiently model at an atomic level. Here, we review emerging atomistic methods to simulate the electrocatalytic interface with special attention devoted to the components/effects that have been challenging to model, such as solvation, electrolyte ions, electrode potential, reaction kinetics, and pH. Additionally, we review relevant computational spectroscopy methods. Then, we showcase several examples of applying these methods to understand and design catalysts relevant to green hydrogen. We also offer experimental views on how to bridge the gap between theory and experiments. Finally, we provide some perspectives on opportunities to advance the field. CONTENTS 3.5. Electrocatalyst Stability 4. Experimental Perspectives 4.1. Experimental Protocols 4.2. Collection and Reporting of Catalytic Activity 4.3. Understanding the Nature of Electrocatalytic Active Sites 4.4.

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“…As noted in the introduction, whenever the interfacial capacitance is independent of the applied potential-as e.g. in many implicit solvent models for high electrolyte concentrations [13,16,68] (see also section 1 in the supporting information (SI) (https://stacks.iop. org/JPCM/33/264004/mmedia))-G α surf in equation ( 1) can be described with a second order polynomial in the number of electrons.…”

Section: Ab Initio Thermodynamics Of Electrochemical Interfacesmentioning

confidence: 99%

Thermodynamic cyclic voltammograms: peak positions and shapes

Hörmann

Reuter

2021

J. Phys.: Condens. Matter

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Based on a mean-field description of thermodynamic cyclic voltammograms (CVs), we analyse here in full generality, how CV peak positions and shapes are related to the underlying interface energetics, in particular when also including electrostatic double layer (DL) effects. We show in particular, how non-Nernstian behaviour is related to capacitive DL charging, and how this relates to common adsorbate-centered interpretations such as a changed adsorption energetics due to dipole-field interactions and the electrosorption valency --the number of exchanged electrons upon electrosorption per adsorbate. Using Ag(111) in halide-containing solutions as test case, we demonstrate that DL effects can introduce peak shifts that are already explained by rationalizing the interaction of isolated adsorbates with the interfacial fields, while alterations of the peak shape are mainly driven by the coverage-dependence of the adsorbate dipoles. In addition, we analyse in detail how changing the experimental conditions such as the ion concentrations in the solvent but also of the background electrolyte can affect the CV peaks via their impact on the potential drop in the DL and the DL capacitance, respectively. These results suggest new routes to analyse experimental CVs and use of those for a detailed assessment of the accuracy of atomistic models of electrified interfaces e.g. with and without explicitly treated interfacial solvent and/or approximate implicit solvent models. File list (2) download file view on ChemRxiv CVs_mainArticle.pdf (724.01 KiB) download file view on ChemRxiv CVs_SupportingInformation.pdf (1.99 MiB)

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Continuum Embedding Models for Electrolyte Solutions in First‐Principles Simulations of Electrochemistry

Cited by 4 publications

References 107 publications

Thermodynamic Cyclic Voltammograms Based onAb InitioCalculations: Ag(111) in Halide-Containing Solutions

Thermodynamic Cyclic Voltammograms Based onAb InitioCalculations: Ag(111) in Halide-Containing Solutions

Emerging Atomistic Modeling Methods for Heterogeneous Electrocatalysis

Thermodynamic cyclic voltammograms: peak positions and shapes

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