Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations

Sundararaman, Ravishankar; Letchworth‐Weaver, Kendra; Schwarz, Kathleen

doi:10.1063/1.5024219

Cited by 58 publications

(106 citation statements)

References 45 publications

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“…Also in this case, a nonlocal definition of the interface may be used to overcome such a limitation. Alternatively, local interfaces that also depend on the electrostatic field [48,50,94,95] have been proposed in the literature and were shown to improve the description of charged systems.…”

Section: Local Vs Nonlocal Interfacesmentioning

confidence: 99%

“…Also in this case, the parameters of the continuum interface describing the electrolyte needs to be chosen with care, as they are strictly linked to the final accuracy of the calculations. [48] For this purpose, Ringe et al proposed a very sensible strategy, based on the calculation of Setschenow coefficients for molecular solutes, which are related to the changes in solvation free energies as a function of the ionic strength (ie, electrolyte concentration). [66] 5 | PERSPECTIVES…”

Section: Modeling Electro-chemistrymentioning

confidence: 99%

“…Pushed by the same motivations behind the FG developments, but following a different path, Arias and coworkers proposed a series of embedding models to approximate classical liquid environments coupled with a first-principles description of the embedded system. [29,33,34,[39][40][41][42][43][44][45][46][47][48] The core of these developments lies in the combination of classical density functional theory of liquid systems with the density functional theory of electrons in quantum-mechanical calculations. The resulting joint-DFT approach provides a very appealing and formal justification of continuum embedding models in terms of the classical statistical description of liquids.…”

mentioning

confidence: 99%

“…Similarly to the FG-derived models, in these joint-DFT approaches a significant effort has been devoted to the modeling of the electrochemical double layer, for which different extensions have been proposed and tested in recent years. [33,[48][49][50] In the context of modeling solvent and electrolyte effects in condensed matter simulations, it is worth mentioning the effective screening medium (ESM) model of Otani and Sugino. [30] In this approach a homogeneous planar dielectric or metal interface is introduced into a slab model of a charged QM substrate.…”

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confidence: 99%

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Continuum embeddings in condensed‐matter simulations

Andreussi

Fisicaro

2018

Int J of Quantum Chemistry

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Continuum models have a long tradition in computational chemistry, where they have provided a compact and efficient way to characterize environment effects in quantum-mechanical simulations of solvated systems. Fattebert and Gygi pioneered the development of continuum dielectric embedding schemes for periodic systems and their seamless extension toward molecular dynamics simulations. Following their work, continuum embedding approaches in condensedmatter simulations have thrived. The possibility to model wet and electrified interfaces, with a reduced computational overhead with respect to isolated systems, is opening new perspectives in the characterization of materials and devices. Important applications of these new techniques are in the field of catalysis, electro-chemistry, electro-catalysis, etc. Here we will address the main physical and computational aspects of continuum embedding schemes recently developed for condensed-matter simulations, underlying their peculiarities and their differences with respect to the quantum-chemistry state-of-the-art.condensed matter, continuum models, electro-chemistry, materials, solvation 1 | INTRODUCTION An embedding liquid environment can substantially affect the electronic properties, geometries and spectroscopic responses of the embedded system. Dealing with this kind of effects is a difficult computational task, due to the multiscale nature of the system. A brute force approach to handle these effects would require including all of the solvent atomistic details in the quantum-mechanical (QM) calculation of the solvated system. The total number of degrees of freedom, in particular the number of electrons that need to be described in a first-principles calculation, can thus increase by orders of magnitude. As a result, a calculation that would be feasible in vacuum can easily become untreatable in solution. Moreover, statistical sampling and averaging of the results over different configurations of the liquid would be required, thus further increasing the computational cost of such an approach. These limitations have motivated the development of incredibly powerful simulation programs, [1][2][3] able to take advantage of the rapid evolution of scientific computing hardware and software, for example, by fully exploiting parallel and hybrid architectures. Regardless of its computational feasibility, the explicit description of liquid environments may also suffer from some well-known limitations of current state-of-the-art ab initio methods, in particular regarding their structural [4][5][6][7] and dielectric [8][9][10] properties.On the other hand, when looking at the properties of a solvated system, it is often the case that the detailed effects caused by solute-solvent interactions are less important than the intrinsic properties of the solute. If this is the case, one can exploit a hierarchical approach, where solvent degrees of freedom are treated with a computationally less expensive technique, but are coupled with an highly accurate description of the solvated system...

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Section: Local Vs Nonlocal Interfacesmentioning

confidence: 99%

Section: Modeling Electro-chemistrymentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Continuum embeddings in condensed‐matter simulations

Andreussi

Fisicaro

2018

Int J of Quantum Chemistry

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“…In computational electrocatalysis adsorbate‐solvent and adsorbate‐electrolyte interactions at the interface can be evaluated implicitly (where the solvent is modelled as a continuum with certain dielectric constant), explicitly, or through combinations of the two . Furthermore, efforts have been devoted to determine the minimal number of explicit water molecules needed to stabilize a given adsorbate .…”

Section: Computational Detailsmentioning

confidence: 99%

Influence of Van der Waals Interactions on the Solvation Energies of Adsorbates at Pt‐Based Electrocatalysts

et al. 2019

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Solvation can significantly modify the adsorption energy of species at surfaces, thereby influencing the performance of electrocatalysts and liquid‐phase catalysts. Thus, it is important to understand adsorbate solvation at the nanoscale. Here we evaluate the effect of van der Waals (vdW) interactions described by different approaches on the solvation energy of *OH adsorbed on near‐surface alloys (NSAs) of Pt. Our results show that the studied functionals can be divided into two groups, each with rather similar average *OH solvation energies: (1) PBE and PW91; and (2) vdW functionals, RPBE, PBE‐D3 and RPBE‐D3. On average, *OH solvation energies are less negative by ∼0.14 eV in group (2) compared to (1), and the values for a given alloy can be extrapolated from one functional to another within the same group. Depending on the desired level of accuracy, these concrete observations and our tabulated values can be used to rapidly incorporate solvation into models for electrocatalysis and liquid‐phase catalysis.

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