Simulation of Adsorption Processes at Metallic Interfaces: An Image Charge Augmented QM/MM Approach

Golze, Dorothea; Iannuzzi, Marcella; Nguyen, Manh‐Thuong; Passerone, Daniele; Hutter, Jürg

doi:10.1021/ct400698y

Cited by 70 publications

(78 citation statements)

References 69 publications

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“…Also, it was shown that the electrostatic energy is almost independent of small variations in the widths of Gaussian charge distribution. 129 The electrode charges were computed on-the-fly by optimizing the total electrostatic energy via self-consistent iterations. Note that the condition of minimizing the electrostatic energy in this setup is equivalent to imposing a certain potential on the electrode atoms and finding the set of electrode surface charges that satisfy this constrain.…”

Section: Discussionmentioning

confidence: 99%

Non-Faradaic Energy Storage by Room Temperature Ionic Liquids in Nanoporous Electrodes

2015

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The enhancement of non-Faradaic charge and energy density stored by ionic electrolytes in nanostructured electrodes is an intriguing issue of great practical importance for energy storage in electric double layer capacitors. On the basis of extensive molecular dynamics simulations of various carbon-based nanoporous electrodes and room temperature ionic liquid (RTIL) electrolytes, we identify atomistic mechanisms and correlations between electrode/electrolyte structures that lead to capacitance enhancement. In the symmetric electrode setup with nanopores having atomically smooth walls, most RTILs showed up to 50% capacitance increase compared to infinitely wide pore. Extensive simulations using asymmetric electrodes and pores with atomically rough surfaces demonstrated that tuning of electrode nanostructure could lead to further substantial capacitance enhancement. Therefore, the capacitance in nanoporous electrodes can be increased due to a combination of two effects: (i) the screening of ionic interactions by nanopore walls upon electrolyte nanoconfinement, and (ii) the optimization of nanopore structure (volume, surface roughness) to take into account the asymmetry between cation and anion chemical structures.

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Section: Discussionmentioning

confidence: 99%

Non-Faradaic Energy Storage by Room Temperature Ionic Liquids in Nanoporous Electrodes

2015

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“…week ending 7 JULY 2017 (QM þ MM) simulations [47], and explained by 2D hydrogen bonding networks within the surface water layers [46]. Water dipole orientation is expressed as ρ H 2 O cos Ψ, where Ψ is the angle between the water bisector and surface normal [see Fig.…”

Section: Prl 119 016801 (2017) P H Y S I C a L R E V I E W L E T T Ementioning

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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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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“…Recently, a novel method was developed by Golze et al to include the polarization between a molecule and a metallic surface in hybrid quantum mechanics/molecular mechanics calculations. 225 For…”

Section: Image Chargementioning

confidence: 99%

Bicomponent Supramolecular Architectures at the Vacuum–Solid Interface

et al. 2017

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This review aims at giving the readers the basic concepts needed to understand two-dimensional bimolecular organizations at the vacuum–solid interface. The first part describes and analyzes molecules–molecules and molecules–substrates interactions. The current limitations and needs in the understanding of these forces are also detailed. Then, a critical analysis of the past and recent advances in the field is presented by discussing most of the key papers describing bicomponents self-assembly on solid surface in an ultrahigh vacuum environment. These sections are organized by considering decreasing molecule–molecule interaction strengths (i.e. starting from strong directional multiple H bonds up to weaker nondirectional bonds taking into account the increasing fundamental role played by the surface). Finally, we conclude with some research directions (predicting self-assembly, multi-components systems, and nonmetallic surfaces) and potential applications (porous networks and organic surfaces).

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Simulation of Adsorption Processes at Metallic Interfaces: An Image Charge Augmented QM/MM Approach

Cited by 70 publications

References 69 publications

Non-Faradaic Energy Storage by Room Temperature Ionic Liquids in Nanoporous Electrodes

Non-Faradaic Energy Storage by Room Temperature Ionic Liquids in Nanoporous Electrodes

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

Bicomponent Supramolecular Architectures at the Vacuum–Solid Interface

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