Electronic structure calculations of liquid-solid interfaces: Combination of density functional theory and modified Poisson-Boltzmann theory

Jinnouchi, Ryosuke; Anderson, Alfred B.

doi:10.1103/physrevb.77.245417

Cited by 302 publications

(414 citation statements)

References 118 publications

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“…25,26 In particular, electronic structure theory 25 indicates that dipole reorientations of adsorbed water molecules on a Pt 111 surface can result in shifts in the potential of zero charge of up to 3 eV. The heterogeneous relaxation elucidated herein are therefore expected to modulate catalytic activities of metal surfaces.…”

Section: Correlation and Distribution Functionsmentioning

confidence: 99%

Characterizing heterogeneous dynamics at hydrated electrode surfaces

Willard

Limmer

Madden

et al. 2013

The Journal of Chemical Physics

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In models of Pt 111 and Pt 100 surfaces in water, motions of molecules in the first hydration layer are spatially and temporally correlated. To interpret these collective motions, we apply quantitative measures of dynamic heterogeneity that are standard tools for considering glassy systems. Specifically, we carry out an analysis in terms of mobility fields and distributions of persistence times and exchange times. In so doing, we show that dynamics in these systems is facilitated by transient disorder in frustrated two-dimensional hydrogen bonding networks. The frustration is the result of unfavorable geometry imposed by strong metal-water bonding. The geometry depends upon the structure of the underlying metal surface. Dynamic heterogeneity of water on the Pt 111 surface is therefore qualitatively different than that for water on the Pt 100 surface. In both cases, statistics of this adlayer dynamic heterogeneity responds asymmetrically to applied voltage.The behavior of water adjacent to hydrated metal surfaces is central to the physics underlying electrochemistry, and as such there is much theoretical work devoted to this topic. References 1-14 are examples. Our recent work in this area 14 highlighted the role of interfacial properties occurring over nanosecond timescales. In this paper, we examine this dynamics in further detail, considering models of Pt-water interfaces and showing structural relaxations in the water ad-layers proceed exceedingly slowly via mechanisms that are spatially heterogeneous.Strong metal-water bonding forces ad-layer waters into structures that are antithetical to favorable hydrogen bonding. Accordingly, the ad-layers contain defects. Motions are one-to two-orders of magnitude faster in the proximity of these defects than elsewhere on the surface. Further, rearrangements of these defects require coordinated motions of several water molecules. This type of heterogeneous dynamics is common in glass-forming materials. 15,16 Some of the quantitative methods used to successfully interpret such behavior in molecular dynamics models of glass formers 16,17 are used here to elucidate the nature of water dynamics at metal surfaces. ModelAs in our earlier work, 13,14 we carry out molecular dynamics simulations with a surface model of Siepman and Sprik. 12 The model provides an empirical water-metal chemisorption potential. It includes effects of the metal's electronic polarizability and its response to applied voltage across an electrochemical cell. For the model parameters we consider, the electrodes most resemble platinum surfaces 18-21 with water-metal binding energies around 0.4eV and a metal lattice constant of 4.0Å. Consequently when the electrode is exposed to a bulk liquid reservoir, water molecules adsorb to the metal atoms and adopt a) Corresponding author. E-mail: chandler@berkeley.edu orientations that allow for hydrogen bond formation with molecules adsorbed to adjacent lattice sites. Snapshots of the ad-layers formed spontaneously from a slab of liquid water are shown in Panels (...

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Section: Correlation and Distribution Functionsmentioning

confidence: 99%

Characterizing heterogeneous dynamics at hydrated electrode surfaces

Willard

Limmer

Madden

et al. 2013

The Journal of Chemical Physics

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“…7 Alternatively, a combination of explicit water molecules and a continuum description of the electrochemical double-layer could be employed in the spirit of the modified Poisson-Boltzmann equation approach. [11][12][13] Having corrected the charged system absolute energies, the potential dependence of the grand canonical energies is obtained by fitting a parabola to the graph energy vs absolute potential. This quadratic relationship arises because the combined system of atoms and background charge can be interpreted as a capacitor.…”

Section: Construction Of Grand Canonical Energiesmentioning

confidence: 99%

“…In a different approach, Neurock and Filhol 8,9 proposed controlling the electrode potential by adding or removing electrons from the electrode, enabling the calculation of absolute energies on a continuous potential scale using a single supercell size. Numerous variants [10][11][12] to this method have been suggested, which mainly differ in the treatment of the electrolyte or the electrode counter-charge. Recently, the method has also been extended to grand canonical simulations in the framework of joint-density functional theory.…”

Section: Introductionmentioning

confidence: 99%

“…Several methods [5][6][7][8][9][10][11][12][13] have been proposed for correcting quantum chemical calculations to constant electrode potential. The most elegant solution would be to treat electrons in the grand canonical ensemble, that is, to allow the number of electrons to change during the electronic structure self-consistency loop, which is equivalent to connecting the system to a fictitious potentiostat.…”

Section: Introductionmentioning

confidence: 99%

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Ab Initio Electrochemistry: Exploring the Hydrogen Evolution Reaction on Carbon Nanotubes

Holmberg

Laasonen

2015

J. Phys. Chem. C

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Density functional theory (DFT) was employed to investigate the hydrogen evolution reaction (HER) on pristine and nitrogen doped carbon nanotubes (CNTs) in acidic solution. As the reaction is an electrocatalytic surface reaction, an accurate description of HER requires performing simulations under constant electrode potential conditions. To this end, we examined HER at several electrode charges allowing us to determine grand canonical activation energies as a continuous function of electrode potential. By studying the elementary steps of HER -the Volmer, Tafel and Heyrovsky reactions -and by considering hydrogen coverage effects, we found that the Volmer-Heyrovsky mechanism is the predominant HER mechanism on CNTs with the Heyrovsky step being rate-determining. Our results indicated that CNTs are electrochemically active towards HER, which seen as a decrease in activation energies with growing electrode potential, but that the activity is lower than on platinum matching experimental data.Substitutional nitrogen doping did not improve HER activity, and further research is required to determine which nitrogen configurations contribute to the enhanced catalytic activity observed for experimental NCNTs.

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“…One key parameter for Mg battery performancethe electrochemical stability of an electrolytehas become a focus of many experimental and theoretical studies. 2−7 The electrochemical stability of the electrolyte is largely an interfacial phenomenon whose description requires a proper handling of the absolute reference for oxidation/reduction potentials, 8−19 the accounting for the screening of charged systems, 11,12,20 and the electrode potential dependent renormalization of the quasiparticle gap of a molecule coupled to a metal surface 21−23 as well as the establishing of voltage dependence of the chemical reactions, their pathways, and transition states. 15,24,25 Accounting for the effects of solvent on the electrolyte stability constitutes another challenge for theoretical studies.…”

Section: ■ Introductionmentioning

confidence: 99%

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)₂ in Diglyme: Implications for Multivalent Electrolytes

2016

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We reveal the general mechanisms of partial reduction of multivalent complex cations in conditions specific for the bulk solvent and in the vicinity of the electrified metal electrode surface and disclose the factors affecting the reductive stability of electrolytes for multivalent electrochemistry. Using a combination of ab initio techniques, we clarify the relation between the reductive stability of contact-ion pairs comprising a multivalent cation and a complex anion, their solvation structures, solvent dynamics, and the electrode overpotential. We found that for ion pairs with multiple configurations of the complex anion and the Mg cation whose available orbitals are partially delocalized over the molecular complex and have antibonding character, the primary factor of the reductive stability is the shape factor of the solvation sphere of the metal cation center and the degree of the convexity of a polyhedron formed by the metal cation and its coordinating atoms. We focused specifically on the details of Mg (II) bis(trifluoromethanesulfonyl)imide in diethylene glycol dimethyl ether (Mg(TFSI)2)/diglyme) and its singly charged ion pair, MgTFSI+. In particular, we found that both stable (MgTFSI)+ and (MgTFSI)0 ion pairs have the same TFSI configuration but drastically different solvation structures in the bulk solution. This implies that the MgTFSI/dyglyme reductive stability is ultimately determined by the relative time scale of the solvent dynamics and electron transfer at the Mg–anode interface. In the vicinity of the anode surface, steric factors and hindered solvent dynamics may increase the reductive stability of (MgTFSI)+ ion pairs at lower overpotential by reducing the metal cation coordination, in stark contrast to the reduction at high overpotential accompanied by TFSI decomposition. By examining other solute/solvent combinations, we conclude that the electrolytes with highly coordinated Mg cation centers are more prone to reductive instability due to the chemical decomposition of the anion or solvent molecules. The obtained findings disclose critical factors for stable electrolyte design and show the role of interfacial phenomena in reduction of multivalent ions.

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Electronic structure calculations of liquid-solid interfaces: Combination of density functional theory and modified Poisson-Boltzmann theory

Cited by 302 publications

References 118 publications

Characterizing heterogeneous dynamics at hydrated electrode surfaces

Characterizing heterogeneous dynamics at hydrated electrode surfaces

Ab Initio Electrochemistry: Exploring the Hydrogen Evolution Reaction on Carbon Nanotubes

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)₂ in Diglyme: Implications for Multivalent Electrolytes

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Electronic structure calculations of liquid-solid interfaces: Combination of density functional theory and modified Poisson-Boltzmann theory

Cited by 302 publications

References 118 publications

Characterizing heterogeneous dynamics at hydrated electrode surfaces

Characterizing heterogeneous dynamics at hydrated electrode surfaces

Ab Initio Electrochemistry: Exploring the Hydrogen Evolution Reaction on Carbon Nanotubes

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)2 in Diglyme: Implications for Multivalent Electrolytes

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Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)₂ in Diglyme: Implications for Multivalent Electrolytes