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A major challenge in the molecular simulation of electric double layer capacitors (EDLCs) is the choice of an appropriate model for the electrode. Typically, in such simulations the electrode surface is modeled using a uniform fixed charge…

Computational Physics · Physics 2015-06-22 Zhenxing Wang , Yang Yang , David L. Olmsted , Mark Asta , Brian B. Laird

Constant potential methods (CPM) enable computationally efficient simulations of the solid-liquid interface at conducting electrodes in molecular dynamics (MD). They have been successfully used, for example, to realistically model the…

Chemical Physics · Physics 2022-07-29 Ludwig J. V. Ahrens-Iwers , Mathijs Janssen , Shern R. Tee , Robert H. Meißner

Constant potential method molecular dynamics simulation (CPM MD) enables the accurate modelling of atomistic electrode charges when studying the electrode-electrolyte interface at the nanoscale. Here we extend the theoretical framework of…

Materials Science · Physics 2023-05-26 Shern Ren Tee , Debra J. Searles

Constant-potential molecular dynamics (MD) simulations are indispensable for understanding the capacitance, structure, and dynamics of electrical double layers (EDLs) at the atomistic level. However, the classical constant-potential method,…

Ab initio modeling of electrochemical systems is becoming a key tool for understanding and predicting electrochemical behavior. Development and careful benchmarking of computational electrochemical methods are essential to ensure their…

Chemical Physics · Physics 2017-03-01 Ravishankar Sundararaman , Kathleen Schwarz

The constant potential molecular dynamics simulation method proposed by Siepmann and Sprik and reformulated later by Reed (SR-CPM) has been widely employed to investigate the metallic electrolyte/electrode interfaces, especially for…

Chemical Physics · Physics 2022-05-04 Haoyu Li , Peiyao Wang , Jefferson Zhe Liu , Gengping Jiang

The development of advanced electrochemical devices for energy conversion and storage requires fine tuning of electrode reactions, which can be accomplished by altering the electrode/solution interface structure. Particularly, in case of an…

Soft Condensed Matter · Physics 2020-07-02 Yu. A. Budkov , A. V. Sergeev , S. V. Zavarzin , A. L. Kolesnikov

Modelling electrolytes accurately on both a nanoscale and cell level can contribute to improving battery chemistries.[Armand and Tarascon, Nature, 2008, 451, 652-657] We previously presented a thermodynamic continuum model for…

Chemical Physics · Physics 2024-08-09 Constantin Schwetlick , Max Schammer , Arnulf Latz , Birger Horstmann

Molecular dynamics (MD) simulations of complex electrochemical systems, such as ionic liquid supercapacitors, are increasingly including the constant potential method (CPM) to model conductive electrodes at specified potential difference,…

Materials Science · Physics 2022-05-13 Shern R. Tee , Debra J. Searles

We formulate a general mean-field theory of a flat electric double layer in ionic liquids and electrolyte solutions with ions possessing static polarizability and a permanent dipole moment on a charged electrode. We establish a new…

Statistical Mechanics · Physics 2021-08-17 Yu. A. Budkov , S. V. Zavarzin , A. L. Kolesnikov

Aqueous lithium chloride solutions up to very high concentrations were investigated in classical molecular dynamics simulations. Various force fields based on the 12-6 Lennard-Jones model, parametrized for non-polarizable water solvent…

Soft Condensed Matter · Physics 2017-07-31 Ildikó Pethes

A better understanding of interfacial mechanisms is needed to improve the performances of electrochemical devices. Yet, simulating an electrode surface at fixed electrolyte composition remains a challenge. Here we apply a finite electric…

Materials Science · Physics 2019-11-13 Thomas Dufils , Guillaume Jeanmairet , Benjamin Rotenberg , Michiel Sprik , Mathieu Salanne

Electrical double layer (EDL) is formed when an electrode is in contact with an electrolyte solution, and is widely used in biophysics, electrochemistry, polymer solution and energy storage. Poisson-Boltzmann (PB) coupled equations provides…

Mesoscale and Nanoscale Physics · Physics 2022-03-02 Cherq Chua , Chun Yun Kee , L. K. Ang , Yee Sin Ang

Climate emergency has led to the investigation of CO$_{2}$ valorization routes. A competitive process included in this framework is the catalytic CO$_{2}$ cycloaddition to epoxides, to produce cyclic carbonates. Halide-based Ionic liquids…

Soft Condensed Matter · Physics 2025-03-17 Sergio Dorado-Alfaro , Elisa Hernández , Jesús Algaba , Pablo Navarro , Felipe J. Blas , José Palomar

Understanding the response of the surface of metallic solids to external electric field sources is crucial to characterize electrode-electrolyte interfaces. Continuum electrostatics offer a simple description of the induced charge density…

Chemical Physics · Physics 2021-12-14 Giovanni Pireddu , Laura Scalfi , Benjamin Rotenberg

Tasker type III polar terminations of ionic crystals carry a net surface charge as well as a dipole moment and are fundamentally unstable. In contact with electrolytes, such polar surfaces can be stabilized by adsorption of counter ions…

Chemical Physics · Physics 2019-03-22 Thomas Sayer , Michiel Sprik , Chao Zhang

Molecular dynamics simulations at a constant electric potential are an essential tool to study electrochemical processes, providing microscopic information on the structural, thermodynamic, and dynamical properties. Despite the numerous…

Ionic liquids are widely used as electrolytes in electrochemical devices. In this context, many experimental and theoretical approaches have been recently developed for characterizing their interface with electrodes. In this perspective…

Materials Science · Physics 2017-09-13 Céline Merlet , Benjamin Rotenberg , Paul Madden , Mathieu Salanne

Many important applications of electronic structure methods involve molecules or solid surfaces in a solvent medium. Since explicit treatment of the solvent in such methods is usually not practical, calculations often employ continuum…

Chemical Physics · Physics 2015-02-12 Ravishankar Sundararaman , William A. Goddard

We propose a simple linear scaling expression in reciprocal space for evaluating the ion--electron potential of crystalline solids. The expression replaces the long-range ion--electron potential with an equivalent localized charge…

Materials Science · Physics 2016-12-21 Xuecheng Shao , Wenhui Mi , Qiang Xu , Yanchao Wang , Yanming Ma
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