Thermodynamic cyclic voltammograms: peak positions and shapes

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

Field Effects at Protruding Defect Sites in Electrocatalysis at Metal Electrodes?

Potential dependencies of adsorption energies at metal electrodes are often interpreted in terms of a dipole-field interaction picture. Classical electrostatics would then suggest particularly strong dependencies at protruding defect sites like steps and kinks due to a local field enhancement. Here, we use first-principles density functional theory calculations that capture the capacitive charging of the electric double layer to analyze these dependencies for prototypical adsorbates at vicinal Pt(111) surfaces in an implicit aqueous electrolyte. This analysis confirms effective dipole-field-type dependencies but rationalizes why they can neither be estimated on the basis of accessible molecular dipoles nor the mere atomic-scale geometry of the adsorption site. The observed magnitude questions mechanistic analyses of surface catalytic reactions made on the basis of the prevalent computational hydrogen electrode approach that is agnostic to these potential-induced adsorption energy variations

Electrosorption at metal surfaces from first principles

Electrosorption of solvated species at metal electrodes is a most fundamental class of processes in interfacial electrochemistry. Here, we use its sensitive dependence on the electric double layer to assess the performance of ab initio thermodynamics approaches increasingly used for the first-principles description of electrocatalysis. We show analytically that computational hydrogen electrode calculations at zero net-charge can be understood as a first-order approximation to a fully grand canonical approach. Notably, higher-order terms in the applied potential caused by the charging of the double layer include contributions from adsorbate-induced changes in the work function and in the interfacial capacitance. These contributions are essential to yield prominent electrochemical phenomena such as non-Nernstian shifts of electrosorption peaks and non-integer electrosorption valencies. We illustrate this by calculating peak shifts for H on Pt electrodes and electrosorption valencies of halide ions on Ag electrodes, obtaining qualitative agreement with experimental data already when considering only second order terms. The results demonstrate the agreement between classical electrochemistry concepts and a first-principles fully grand canonical description of electrified interfaces and shed new light on the widespread computational hydrogen electrode approach

Dynamic structure factor of the antiferromagnetic Kitaev model in large magnetic fields

We investigate the dynamic structure factor of the antiferromagnetic Kitaev honeycomb model in a magnetic field by applying perturbative continuous unitary transformations about the high-field limit. One- and two-quasi-particle properties of the dressed elementary spin flip excitations of the high-field polarized phase are calculated which account for most of the spectral weight in the dynamic structure factor. We discuss the evolution of spectral features in these quasi-particle sectors in terms of one-quasi-particle dispersions, two-quasi-particle continua, the formation of anti-bound states, and quasi-particle decay. In particular, a comparably strong spectral feature above the upper edge of the upmost two-quasi-particle continuum represents three anti-bound states which form due to nearest-neighbor density-density interactions.Comment: 14 pages, 10 figure

Implicit Solvation Methods for Catalysis at Electrified Interfaces

Implicit solvation is an effective, highly coarse-grained approach in atomic-scale simulations to account for a surrounding liquid electrolyte on the level of a continuous polarizable medium. Originating in molecular chemistry with finite solutes, implicit solvation techniques are now increasingly used in the context of first-principles modeling of electrochemistry and electrocatalysis at extended (often metallic) electrodes. The prevalent ansatz to model the latter electrodes and the reactive surface chemistry at them through slabs in periodic boundary condition supercells brings its specific challenges. Foremost this concerns the difficulty of describing the entire double layer forming at the electrified solid–liquid interface (SLI) within supercell sizes tractable by commonly employed density functional theory (DFT). We review liquid solvation methodology from this specific application angle, highlighting in particular its use in the widespread ab initio thermodynamics approach to surface catalysis. Notably, implicit solvation can be employed to mimic a polarization of the electrode’s electronic density under the applied potential and the concomitant capacitive charging of the entire double layer beyond the limitations of the employed DFT supercell. Most critical for continuing advances of this effective methodology for the SLI context is the lack of pertinent (experimental or high-level theoretical) reference data needed for parametrization

Ising model in a light-induced quantized transverse field

We investigate the influence of light-matter interactions on correlated quantum matter by studying the paradigmatic Dicke-Ising model. This type of coupling to a confined, spatially delocalized bosonic light mode, such as provided by an optical resonator, resembles a quantized transverse magnetic field of tunable strength. As a consequence, the symmetry-broken magnetic state breaks down for strong enough light-matter interactions to a paramagnetic state. The nonlocal character of the bosonic mode can change the quantum phase transition in a drastic manner, which we analyze quantitatively for the simplest case of the Dicke-Ising chain geometry. The results show a direct transition between a magnetically ordered phase with zero photon density and a magnetically polarized phase with superradiant behavior of the light. Our predictions are equally valid for the dual quantized Ising chain in a conventional transverse magnetic field

Static and dynamic water structures at interfaces: A case study with focus on Pt(111)

An accurate atomistic treatment of aqueous solid–liquid interfaces necessitates the explicit description of interfacial water ideally via ab initio molecular dynamics simulations. Many applications, however, still rely on static interfacial water models, e.g., for the computation of (electro)chemical reaction barriers and focus on a single, prototypical structure. In this work, we systematically study the relation between density functional theory-derived static and dynamic interfacial water models with specific focus on the water–Pt(111) interface. We first introduce a general construction protocol for static 2D water layers on any substrate, which we apply to the low index surfaces of Pt. Subsequently, we compare these with structures from a broad selection of reference works based on the Smooth Overlap of Atomic Positions descriptor. The analysis reveals some structural overlap between static and dynamic water ensembles; however, static structures tend to overemphasize the in-plane hydrogen bonding network. This feature is especially pronounced for the widely used low-temperature hexagonal ice-like structure. In addition, a complex relation between structure, work function, and adsorption energy is observed, which suggests that the concentration on single, static water models might introduce systematic biases that are likely reduced by averaging over consistently created structural ensembles, as introduced here

CMS Barrel Pixel Detector Overview

The pixel detector is the innermost tracking device of the CMS experiment at the LHC. It is built from two independent sub devices, the pixel barrel and the end disks. The barrel consists of three concentric layers around the beam pipe with mean radii of 4.4, 7.3 and 10.2 cm. There are two end disks on each side of the interaction point at 34.5 cm and 46.5 cm. This article gives an overview of the pixel barrel detector, its mechanical support structure, electronics components, services and its expected performance.Comment: Proceedings of Vertex06, 15th International Workshop on Vertex Detector