Communication: Computing the Helmholtz capacitance of charged insulator-electrolyte interfaces from the supercell polarization.

  title={Communication: Computing the Helmholtz capacitance of charged insulator-electrolyte interfaces from the supercell polarization.},
  author={Chao Mo Zhang},
  journal={The Journal of chemical physics},
  volume={149 3},
  • C. Zhang
  • Published 1 May 2018
  • Physics, Medicine
  • The Journal of chemical physics
Supercell modeling of an electrical double layer (EDL) at electrified solid-electrolyte interfaces is a challenge. The net polarization of EDLs arising from the fixed chemical composition setup leads to uncompensated EDLs under periodic boundary condition and convolutes the calculation of the Helmholtz capacitance [C. Zhang and M. Sprik, Phys. Rev. B 94, 245309 (2016)]. Here we provide a new formula based on the supercell polarization at zero electric field Ē = 0 (i.e., standard Ewald boundary… Expand
8 Citations
Coupling of Surface Chemistry and Electric Double Layer at TiO2 Electrochemical Interfaces.
P pH-dependence of the Helmholtz capacitance at electrified rutile TiO2 (110)-NaCl electrolyte interfaces is investigated and it is found that, due to competing forces from surface adsorption and from electric double layer, water molecules have a stronger structural fluctuation at high pH and this leads to a much larger capacitance. Expand
Effective Dielectric Constant of Water at the Interface with Charged C60 Fullerenes.
The dipolar susceptibility of interfacial water and the corresponding interface dielectric constant were calculated from numerical molecular dynamics simulations for neutral and charged states of buckminsterfullerene C60 and are consistent with recent reports for biological and nanometer-scale interfaces. Expand
DFT-MD of the (110)-Co3O4 cobalt oxide semiconductor in contact with liquid water, preliminary chemical and physical insights into the electrochemical environment.
A detailed characterization of the chemical and physical properties of the aqueous interface is provided in terms of structure, dynamics, electric field, work function, and spectroscopy, as a preliminary step into the modelling of the (110)-Co3O4 aQueous surface in more relevant electrochemical conditions. Expand
Stabilization of AgI's polar surfaces by the aqueous environment, and its implications for ice formation.
  • T. Sayer, S. Cox
  • Medicine, Physics
  • Physical chemistry chemical physics : PCCP
  • 2019
This simulation study investigates to what extent the surrounding aqueous environment is able to provide polarity compensation and finds that pure H2O is unable to stabilize the AgI crystal in a physically reasonable manner, and that mobile charge carriers such as dissolved ions are essential. Expand
Modelling electrochemical systems with finite field molecular dynamics
Physical chemistry of electric double layers and ionic solutions plays a fundamental role in energy related applications such as electrocatalysis, super-capacitors, fuel cells, lithium/sodium ion bExpand
Control of Electrical and Optical Parameters of Humidity Sensors Active Elements Based on Tin Oxides Films with Variable Composition
The aim of this work is development of technique for synthesis of tin oxides films with various stoichiometric composition, characterized by high electrical conductivity and light transmittance inExpand
Управление электрическими и оптическими параметрами активных элементов датчиков влажности на основе пленок оксидов олова переменного состава
The aim of this work is development of technique for synthesis of tin oxides films with various stoichiometric composition, characterized by high electrical conductivity and light transmittance inExpand
Macroscopic surface charges from microscopic simulations.
  • T. Sayer, S. Cox
  • Materials Science, Physics
  • The Journal of chemical physics
  • 2020
It is demonstrated that, in the slab geometry typically used in simulations, imposing an electric displacement field D determines the integrated surface charge density of adsorbed ions at charged interfaces, which allows for macroscopic surface charge densities irrespective of the slab thickness used in the authors' simulations. Expand


Finite field methods for the supercell modeling of charged insulator/electrolyte interfaces
Interactions between aligned dipoles in periodic model systems are often considered spurious and removed by partitioning the supercell in isolated slabs separated by vacuum layers. One popular andExpand
Charge compensation at the interface between the polar NaCl(111) surface and a NaCl aqueous solution.
A generalized Helmholtz capacitance CH is defined which can be computed by varying the applied electric field and it is verified that the excess electrolyte ionic charge at the interface conforms to the Tasker 1/2 rule for compensating charge in the theory of polar rock salt (111) surfaces. Expand
Inversion of the Electric Field at the Electrified Liquid-Liquid Interface.
The thermodynamics of the general system of two immiscible electrolytes in the presence of an electric field depends strongly on the distribution of ions near the liquid interface, which is calculated via Monte Carlo simulations, which include ion correlations and polarization effects, and via a modified nonlinear Poisson-Boltzmann theory. Expand
Molecular Dynamics Study of the Electrical Double Layer at Silver Chloride Electrolyte Interfaces
Molecular dynamics simulations of the electrical double layer at AgCl−aqueous electrolyte (KCl) interfaces are presented, accompanied by a new force field and properties of bulk AgCl computed usingExpand
The electric double layer at a rutile TiO₂ water interface modelled using density functional theory based molecular dynamics simulation.
  • J. Cheng, M. Sprik
  • Chemistry, Medicine
  • Journal of physics. Condensed matter : an Institute of Physics journal
  • 2014
A fully atomistic model of a compact electric double layer at the rutile TiO2(1 1 0)-water interface is constructed by adding protons to bridging oxygens or removing them from H2O molecules adsorbedExpand
Ionic liquid near a charged wall: structure and capacitance of electrical double layer.
We study the effects of ion size asymmetry and short-range correlations on the electrical double layer in ionic liquids: we perform molecular dynamics simulations of a model ionic liquid between twoExpand
Electrical properties of polarizable ionic solutions. I. Theoretical aspects
We generalize previous work [J. Chem. Phys. 85, 6645 (1986)] on the relation between the frequency‐dependent dielectric constant and conductivity and time correlation functions of electrical currentExpand
Molecular dynamics simulations of the electrical double layer at the 1 M KCl solution | Hg electrode interface
Abstract In this work we present the results of molecular dynamics simulations of the electrical double layer (edl) of a metal ∣ electrolyte solution (Hg ∣ 1.0 M KCl) interface at three differentExpand
Electric displacement as the fundamental variable in electronic-structure calculations
Finite-field calculations in periodic insulators are technically and conceptually challenging, owing to fundamental problems in defining polarization in extended solids. Although significant progressExpand
How Ion Condensation Occurs at a Charged Surface: A Molecular Dynamics Investigation of the Stern Layer for Water–Silica Interfaces
We investigate the Stern layer of charged silica–water interfaces by calculating the ion–surface interaction from molecular dynamics simulations. The McMillan–Mayer potentials of mean force between aExpand