Multiscale Modeling of Aqueous Electric Double Layers

Chemical Reviews, Год журнала: 2023, Номер 124(1), С. 1 - 26

Опубликована: Дек. 20, 2023

From the stability of colloidal suspensions to charging electrodes, electric double layers play a pivotal role in aqueous systems. The interactions between interfaces, water molecules, ions and other solutes making up electrical layer span length scales from Ångströms micrometers are notoriously complex. Therefore, explaining experimental observations terms layer's molecular structure has been long-standing challenge physical chemistry, yet recent advances simulations techniques computational power have led tremendous progress. In particular, past decades seen development multiscale theoretical framework based on combination quantum density functional theory, force-field continuum theory. this Review, we discuss these developments make quantitative comparisons results from, among techniques, sum-frequency generation, atomic-force microscopy, electrokinetics. Starting vapor/water interface, treat range qualitatively different types surfaces, varying soft solid, hydrophilic hydrophobic, charged uncharged.

Язык: Английский

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An implicit electrolyte model for plane wave density functional theory exhibiting nonlinear response and a nonlocal cavity definition

The Journal of Chemical Physics, Год журнала: 2023, Номер 159(23)

Опубликована: Дек. 19, 2023

We have developed and implemented an implicit electrolyte model in the Vienna Ab initio Simulation Package (VASP) that includes nonlinear dielectric ionic responses as well a nonlocal definition of cavities defining spatial regions where these can occur. The implementation into existing VASPsol code is numerically efficient exhibits robust convergence, requiring computational effort only slightly higher than original linear polarizable continuum model. + able to reproduce characteristic "double hump" shape observed experimentally for differential capacitance electrified metal interface while preventing "leakage" space too small contain single water molecule or solvated ion. also gives reasonable prediction molecular solvation free energies self-ionization energy absolute electron chemical potential standard hydrogen electrode. All this, combined with additional ability run constant density functional theory calculations, should enable routine computation activation barriers electrocatalytic processes.

Язык: Английский

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Construction of High Accuracy Machine Learning Interatomic Potential for Surface/Interface of Nanomaterials—A Review

Advanced Materials, Год журнала: 2023, Номер 36(22)

Опубликована: Авг. 28, 2023

Abstract The inherent discontinuity and unique dimensional attributes of nanomaterial surfaces interfaces bestow them with various exceptional properties. These properties, however, also introduce difficulties for both experimental computational studies. advent machine learning interatomic potential (MLIP) addresses some the limitations associated empirical force fields, presenting a valuable avenue accurate simulations these surfaces/interfaces nanomaterials. Central to this approach is idea capturing relationship between system configuration energy, leveraging proficiency (ML) precisely approximate high‐dimensional functions. This review offers an in‐depth examination MLIP principles their execution elaborates on applications in realm surface interface systems. prevailing challenges faced by potent methodology are discussed.

Язык: Английский

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Accurate Fourth-Generation Machine Learning Potentials by Electrostatic Embedding

Journal of Chemical Theory and Computation, Год журнала: 2023, Номер 19(12), С. 3567 - 3579

Опубликована: Июнь 8, 2023

In recent years, significant progress has been made in the development of machine learning potentials (MLPs) for atomistic simulations with applications many fields from chemistry to materials science. While most current MLPs are based on environment-dependent atomic energies, limitations this locality approximation can be overcome, e.g., fourth-generation MLPs, which incorporate long-range electrostatic interactions an equilibrated global charge distribution. Apart considered interactions, quality crucially depends information available about system, i.e., descriptors. work we show that including─in addition structural information─the potential arising distribution environments significantly improves and transferability potentials. Moreover, extended descriptor allows two- three-body feature vectors overcome regarding artificially degenerate environments. The capabilities such electrostatically embedded high-dimensional neural network (ee4G-HDNNP), is further augmented by pairwise demonstrated NaCl as a benchmark system. Employing data set containing only neutral negatively charged clusters, even small energy differences between different cluster geometries resolved, shows impressive positively clusters well melt.

Язык: Английский

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Molecular dynamics simulations of electrochemical interfaces

The Journal of Chemical Physics, Год журнала: 2023, Номер 159(9)

Опубликована: Сен. 6, 2023

Molecular dynamics (MD) simulations have become a powerful tool for investigating electrical double layers (EDLs), which play crucial role in various electrochemical devices. In this Review, we provide comprehensive overview of the techniques used MD EDL studies, with particular focus on methods describing electrode polarization, and examine principle behind these their varying applicability. The applications approaches supercapacitors, capacitive deionization, batteries, electric double-layer transistors are explored, highlighting recent advancements insights each field. Finally, emphasize challenges potential directions future developments EDLs, such as considering movable electrodes, improving property representation, incorporating chemical reactions, enhancing computational efficiency to deepen our understanding complex processes contribute progress field involving EDLs.

Язык: Английский

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Advanced carbon as emerging energy materials in lithium batteries: A theoretical perspective

InfoMat, Год журнала: 2025, Номер unknown

Опубликована: Янв. 14, 2025

Abstract Lithium batteries are becoming increasingly vital thanks to electric vehicles and large‐scale energy storage. Carbon materials have been applied in battery cathode, anode, electrolyte, separator enhance the electrochemical performance of rechargeable lithium batteries. Their functions cover storage, catalysis, electrode protection, charge conduction, so on. To rationally implement carbon materials, their properties interactions with other probed by theoretical models, namely density functional theory molecular dynamics. This review summarizes use models guide employment advanced batteries, providing critical information difficult or impossible obtain from experiments, including lithiophilicity, barriers, coordination structures, species distribution at interfaces. under discussion include zero‐dimensional fullerenes capsules, one‐dimensional nanotubes nanoribbons, two‐dimensional graphene, three‐dimensional graphite amorphous carbon, as well derivatives. electronic conductivities explored, followed applications cathode anode performance. While role is emphasized, experimental data also touched upon clarify background show effectiveness strategies. Evidently, prove promising achieving superior density, rate performance, cycle life, especially when informed endeavors. image

Язык: Английский

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Constant-Potential Modeling of Electrical Double Layers Accounting for Electron Spillover

Physical Review Letters, Год журнала: 2025, Номер 134(4)

Опубликована: Янв. 28, 2025

Constant-potential molecular dynamics (MD) simulations are indispensable for understanding the structure, capacitance, and of electrical double layers (EDLs) at atomistic level. However, classical constant-potential method, relying on so-called ``fluctuating charges'' to keep electrode equipotential, overlooks quantum effects always underestimates EDL capacitance typical metal aqueous electrolyte interfaces. Here, we propose a constant potential method accounting electron spillover outermost nuclei electrode. For EDLs Au(111) electrodes, our MD simulation reveals bell-shaped curves in magnitude shape both quantitatively consistent with experiments. It unveils electrode-polarization-dependent local electric fields, agreeing experimental observations redshift vibration interfacial water under negative polarization predicting blueshift positive polarization, further identifies geometry dependence two timescales during charging.

Язык: Английский

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Cation effects on CO ₂ reduction catalyzed by single-crystal and polycrystalline gold under well-defined mass transport conditions

Science Advances, Год журнала: 2025, Номер 11(6)

Опубликована: Фев. 7, 2025

The presence of alkali metal cations in the electrolyte substantially affects reactivity and selectivity electrochemical carbon dioxide (CO2) reduction (CO2R). This study examines role CO2R on single-crystal polycrystalline Au under controlled mass-transport conditions. It establishes that CO2 adsorption is rate-determining step regardless cation type or surface structure. Density functional theory calculations show electron transfer occurs to a solvated CO2-cation complex. A more positive potential zero charge enhances activity only with similar coordination. symmetry factor (β) varies structure identity, density indicating β's sensitivity double-layer structures. These findings emphasize importance both structures understanding effects CO2R.

Язык: Английский

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Elucidating Ionic Liquids-Mediated Electrochemical Interfaces for Energy Storage and Electrocatalysis

Materials Today Energy, Год журнала: 2025, Номер unknown, С. 101908 - 101908

Опубликована: Май 1, 2025

Язык: Английский

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Unraveling the reaction mechanisms for furfural electroreduction on copper

EES Catalysis, Год журнала: 2023, Номер 1(4), С. 539 - 551

Опубликована: Янв. 1, 2023

Combining theory and experiment, we unveil the mechanisms for furfural electroreduction on copper provide a rationale to tune reaction conditions increase activity towards value-added products.

Язык: Английский

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