Local order of liquid water at metallic electrode surfaces

Pedroza, Luana S.; Poissier, Adrien; Fernández-Serra, Mariví

doi:10.1063/1.4905493

Cited by 38 publications

(42 citation statements)

References 40 publications

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“…The computed PZC of Pt(111), Au(111), Pd(111) and Ag(111) water interfaces are listed in Table I, Table I shows that there is a similar size of error in the Φ of Pd(111), in line with previous work [15], while the rest of the Φ are as accurate as the PZC predicted by the same PBE functional. This can be best seen from the difference (ΔΦ) between PZC and Φ, which can be regarded as a measure of interface dipole potentials formed by dipping metal surfaces into liquid water.…”

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confidence: 74%

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Determining Potentials of Zero Charge of Metal Electrodes versus the Standard Hydrogen Electrode from Density-Functional-Theory-Based Molecular Dynamics

et al. 2017

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We develop a computationally efficient scheme to determine the potentials of zero charge (PZC) of metal-water interfaces with respect to the standard hydrogen electrode. We calculate the PZC of Pt(111), Au(111), Pd(111) and Ag(111) at a good accuracy using this scheme. Moreover, we find that the interface dipole potentials are almost entirely caused by charge transfer from water to the surfaces, the magnitude of which depends on the bonding strength between water and the metals, while water orientation hardly contributes at the PZC conditions. DOI: 10.1103/PhysRevLett.119.016801 Metal-water interfaces are of great technological importance in many energy storage and conversion devices such as fuel cells and batteries. Fundamentally, they are the primary subjects for studying electrochemical processes (i.e., electrocatalysis and corrosion) in electrochemistry and play a crucial role in the development of electric double layer (EDL) theories (i.e., Gouy-Chapman-Stern model). Direct probing of structures and dynamics of the interfaces at a molecular level is extremely challenging for experiment. First principles simulations, on the other hand, can offer detailed microscopic information on the interfaces. However, due to high computational costs, it was not long ago that ab initio modeling of metal-water interfaces became affordable [1,2].Potential of zero charge (PZC) is a fundamental concept in the EDL theories, defined as the potential at which no excess charge exists on metal surfaces, and deviation from the PZC will lead to attraction of counterions to the surfaces, building up the EDL [3]. Because of its significance to the microscopic understanding of an EDL and interfacial potentials, numerous experimental techniques have been developed to determine the PZC of metal electrodes, e.g., surface tension methods, capacitance measurement methods, CO charge-displacement methods, etc [4]. Despite repeated efforts, many measurements are still subject to uncertainties because of difficulties in preparing single crystal electrodes and excluding specific adsorption of electrolyte ions [5][6][7]. In the presence of specific adsorption, electrochemists distinguish the subtlety between the potential of zero total charge (PZTC) and the potential of zero free charge (PZFC), and only the latter is an intrinsic property of metal electrodes [8].First principles calculation of well-defined metal surfaces is ideal for determining the PZFC. There are two issues in computational methods. First, how is the solvent treated in the simulation models? In the literature, water has often been treated with either an implicit dielectric continuum [9][10][11] or some representations of static water structures for efficiency [12]. It, however, has been reported that the dynamics of water on surfaces has significant effects on interface potentials [13]. As yet, very few studies have modeled full metal-water interfaces and accounted for water dynamics using density functional theory based molecular dynamics (DFTMD) [14,15]. Second, how are th...

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confidence: 74%

“…It, however, has been reported that the dynamics of water on surfaces has significant effects on interface potentials [13]. As yet, very few studies have modeled full metal-water interfaces and accounted for water dynamics using density functional theory based molecular dynamics (DFTMD) [14,15]. Second, how are the computed potentials referenced to?…”

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confidence: 99%

Determining Potentials of Zero Charge of Metal Electrodes versus the Standard Hydrogen Electrode from Density-Functional-Theory-Based Molecular Dynamics

et al. 2017

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“…It is a well-known problem that widely used density functionals based on generalized gradient approximation (GGA), such as the popular Perdew-Becke-Ernzerhof (PBE) functional [11], lead to an over-structuring of liquid water [12,13] compared to experiments [14] which is caused by the over-estimation of the directional hydrogen-bonding in the PBE functional [15]. Still the PBE functional has been used quite frequently to address properties of systems including liquid water [16][17][18][19]. In order to reproduce the structural properties of liquid water at room temperature correctly, the temperature in the molecular dynamics runs has been deliberately raised [16][17][18].…”

Section: Introductionmentioning

confidence: 99%

“…Still the PBE functional has been used quite frequently to address properties of systems including liquid water [16][17][18][19]. In order to reproduce the structural properties of liquid water at room temperature correctly, the temperature in the molecular dynamics runs has been deliberately raised [16][17][18]. Of course, this is not a very satisfactory approach.…”

Section: Introductionmentioning

confidence: 99%

The structure of water at a Pt(111) electrode and the potential of zero charge studied from first principles

Sakong

Forster-Tonigold

Groß

2016

The Journal of Chemical Physics

154

150

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The structure of a liquid water layer on Pt(111) has been studied by ab initio molecular dynamics simulations based on periodic density functional theory calculations. First the reliability of the chosen exchange-correlation function has been validated by considering water clusters, bulk ice structures, and bulk liquid water, confirming that the dispersion corrected RPBE-D3/zero functional is a suitable choice. The simulations at room temperature yield that a water layer that is six layers thick is sufficient to yield liquid water properties in the interior of the water film. Performing a statistical average along the trajectory, a mean work function of 5.01 V is derived, giving a potential of zero charge of Pt(111) of 0.57 V vs. standard hydrogen electrode, in good agreement with experiments. Therefore we propose the RPBE-D3/zero functional as the appropriate choice for first-principles calculations addressing electrochemical aqueous electrolyte/metal electrode interfaces.

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“…[16][17][18][19]23,27,33 Density functional theory (DFT) calculations have predicted that, in vacuo, a single molecule of water adsorbs more strongly at the interface of Pd, and Pt, than to Au and Ag. [34][35][36][37][38] This might lead to a more strongly bound, and ordered, first layer of liquid water molecules at the Pd(111) interface compared with the Au/Ag(111) interface, 33,[39][40][41] which is likely to affect how (bio)molecules adsorb to these different aqueous metal interfaces. Therefore, it is important that our FF can provide a physically reasonable description of the Pd(111)-aqueous interface.…”

Section: Introductionmentioning

confidence: 99%

Distinct Differences in Peptide Adsorption on Palladium and Gold: Introducing a Polarizable Model for Pd(111)

Hughes

Walsh

2018

J. Phys. Chem. C

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Materials-binding peptides offer promising routes to the production of tailored Pd nanomaterials in aqueous media, enabling the optimization of catalytic properties. However, the atomic-scale details needed to make these advances are relatively scarce and challenging to obtain. Molecular simulations can provide key insights into the structure of peptides adsorbed at the aqueous Pd interface, provided that the forcefield can appropriately capture the relevant bio-interface interactions. Here, we introduce and apply a new polarizable force field, PdP-CHARMM, for the simulation of biomolecule-Pd binding under aqueous conditions. PdP-CHARMM was parametrized with density functional theory (DFT) calculations, using a process compatible with similar polarizable force-fields created for Ag and Au surfaces, ultimately enabling a direct comparison of peptide binding modes across these metal substrates. As part of our process for developing PdP-CHARMM, we provide an extensive study of the performance of ten different dispersion-inclusive DFT functionals in recovering biomolecule-Pd(111) binding. We use the functional with best all-round performance to create PdP-CHARMM. We then employ PdP-CHARMM and metadynamics simulations to estimate the adsorption free energy for a range of amino acids at the aqueous Pd(111) interface. Our findings suggest that only His and Met favor direct contact with the Pd substrate, which we attribute to a remarkably robust interfacial solvation layering. Replica-exchange with solute tempering molecular dynamics simulations of two experimentally-identified Pd-binding peptides also indicate surface contact to be chiefly mediated by His and Met residues at aqueous Pd(111). Adsorption of these two peptides was also predicted for the Au(111) interface, revealing distinct differences in both the solvation structure and modes of peptide adsorption at the Au and Pd interfaces. We propose that this sharp contrast in peptide binding is largely due to the differences in interfacial solvent structuring. 2

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Local order of liquid water at metallic electrode surfaces

Cited by 38 publications

References 40 publications

Determining Potentials of Zero Charge of Metal Electrodes versus the Standard Hydrogen Electrode from Density-Functional-Theory-Based Molecular Dynamics

Determining Potentials of Zero Charge of Metal Electrodes versus the Standard Hydrogen Electrode from Density-Functional-Theory-Based Molecular Dynamics

The structure of water at a Pt(111) electrode and the potential of zero charge studied from first principles

Distinct Differences in Peptide Adsorption on Palladium and Gold: Introducing a Polarizable Model for Pd(111)

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