arXiv subjects

Michael Eikerling

Publications and source records attributed to Michael Eikerling.

6 recordsLinked to original sources

arXiv2026

Revealing the Role of Confined Molecular H$_2$ in the Passivation of Defective Silicon Using First-Principles Simulations

The passivation of silicon dangling bonds by hydrogen is a crucial requirement for silicon-based optoelectronic technology, especially for solar cells. Recent experiments on intense light soaking of silicon heterojunction solar cells unveiled interesting dynamical aspects of hydrogen passivation that are linked to Si-H bond breaking and repassivation. These processes take place predominantly in porous regions near the amorphous/crystalline interface, where hydrogen can exist in molecular form. This work addresses the question of whether molecular H$_2$ directly participates in Si-H depassivation and repassivation. Using density functional theory, we calculate and compare formation energies of point defects, multivacancy cavities and the Si(100) surface to identify relevant passivated and depassivated states. Furthermore, we employ nudged elastic band calculations to determine the activation barriers of the corresponding pathways. We find that sufficient local free volume enables a direct double-H pathway for depassivation through the formation of confined molecular H$_2$. Despite involving the breaking of two Si-H bonds, the double-H process can be energetically and kinetically competitive with the single-H process and can exhibit a reverse repassivation barrier as low as $0.15\,$eV under p-type conditions. These findings provide a plausible atomistic explanation for passivation recovery during light soaking and illuminated annealing in porous regions near amorphous/crystalline silicon interfaces.

cond-mat.mtrl-sci↗

arXiv2026

Molecular dynamics simulations of Nafion thin films at a platinum catalyst surface: Correlating structure with charging behaviour

Electrocatalysis is greatly influenced by the local reaction environment, which is governed by the structure of the catalyst, the distribution of the electrolyte, and the local electric field. In catalytic systems comprised of complex molecular species like ionomers, the distribution of electrolyte can vary substantially, resulting in divers local reaction environments. In order to gain atom-scale insight into this micro-environment we construct a model system consisting of a platinum surface, varying levels of water, and a Nafion thin film and conduct molecular dynamics simulations. We employ a construction based on Voronoi tesselation to assemble a dense film of ionomer that fully covers the platinum substrate. An energy analysis reveals that water film configurations with thickness of less then 1.3 nm are stable. Simulations with charged platinum surfaces are analysed in view of electrostatic conditions and differential capacitance of the interface configuration. Trends observed in these properties can be interpreted in view of the crowding of hydronium ions or the Nafion film at the platinum surface. The presented workflow can be easily applied to investigate novel ionomers for use in PEMFCs.

physics.chem-ph↗

arXiv2025

Classical theory of electron-ion correlations at electrochemical interfaces: Closing the circuit from double-layer charging to ion adsorption

The electric double layer (EDL) that forms at the interface between metals and ionic solutions is at the heart of various energy technologies. Recent experimental data have challenged our traditional understanding of the EDL charging behavior, which is based on mean-field Gouy-Chapman-Stern-type (GCS) models. In this article, we present a classical theory for the EDL, derived from first-principles statistical mechanics, that accounts for electron-ion correlation effects using the method of image charges and systematically extends beyond the mean-field level. Such electron-ion correlations introduce an additional interaction between the metal surface and electrolyte ions, significantly altering the EDL structure. Our theory, valid in the limit of dilute electrolyte solutions and weakly charged metal surfaces, achieves quantitative agreement with experimental capacitance data across a wide range of electrode materials and electrolyte solvents, and thus resolves long-standing questions on the origin of discrepancies to GCS predictions. Thereby, the framework conceptually unifies the processes of double-layer charging and ion adsorption (electrosorption), which are typically considered as distinct phenomena, but are shown to be manifestations of the same fundamental electrostatic principles.

cond-mat.stat-mech↗

arXiv2025

Theory of Electro-Ionic Perturbations at Supported Electrocatalyst Nanoparticles

Nanoscopic heterogeneities in composition and structure are quintessential for the properties of electrocatalyst materials. Here, we present a semiclassical model to study the electrochemical properties of supported electrocatalyst nanoparticles (NP). The model captures the correlated electronic and ionic equilibration across NP, support, and electrolyte. It reveals peculiar trends in surface charging of the supported NP, validated by comparison with first-principles calculations. Support-induced perturbations in electronic and ionic charge densities at the NP's active surface manifest as distinct potentials of zero local electronic and ionic charges that could differ by more than 0.5 V in the studied system.

cond-mat.mtrl-sci↗

arXiv2024

Variational functional theory for coulombic correlations in the electric double layer

A classical coulombic correlation functional in one-loop (1L) and local-density-approximation (LDA) is derived for electrolyte solutions, starting from a first-principles many-body partition function. The 1L-LDA functional captures correlations between electrolyte ions and solvent dipoles, such as screening and solvation, that are ignored by conventional mean-field theories. This 1L-LDA functional introduces two parameters that can be tuned to the experimental dielectric permittivity and activity coefficients in the bulk electrolyte solution. The capabilities of the 1L-LDA functional for the description of metal-electrolyte interfaces are demonstrated by embedding the functional into a combined quantum-classical model. Here, the 1L-LDA functional leads to a more pronounced double-peak structure of the interfacial capacitance with higher peaks and shorter peak-to-peak distance, significantly improving the agreement with experimental data and showing that electrolyte correlation effects exert a vital impact on the capacitive response.

physics.chem-ph↗

arXiv2018

Impedance resonance in narrow confinement

The article explores the ion flux response of a capacitor configuration to an alternating voltage. The model system comprises a symmetric binary electrolyte confined between plan-parallel capacitor plates. The AC response is investigated for the sparsely studied albeit practically important case of a large amplitude voltage applied across a narrow device, with the distance between the two plates amounting to a few ion diameters. Dynamic density functional theory is employed to solve for the spatiotemporal ion density distribution as well as the transient ion flux and complex impedance of the system. The analysis of these properties reveals a hitherto hidden impedance resonance. A single ion analogue of the capacitor, which is equivalent to neglecting all interactions between the ions, is employed for a physical interpretation of this phenomenon. It explains the resonance as a consequence of field-induced ion condensation at the capacitor plates and coherent motion of condensed ions in response to the field variation.

physics.chem-ph↗