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First-principles calculations combining density-functional theory and continuum solvation models enable realistic theoretical modeling and design of electrochemical systems. When a reaction proceeds in such systems, the number of electrons…
How does an electrochemical interface respond to changes in the electrode potential? How does the response affect the key properties of the system - energetics, excess charge, capacitance? Essential questions key to ab-initio simulations of…
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…
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…
As interest in nanomaterials grows, ab initio simulations play a crucial role in designing electrochemical catalysts. Electrochemical reactions depend on electrode potential, highlighting the importance of the grand canonical…
Proton-coupled electron transfer (PCET) is the key step for energy conversion in electrocatalysis. Atomic-scale simulation acts as an indispensable tool to provide a microscopic understanding of PCET. However, consideration of the quantum…
Controlling electrochemical reactivity requires a detailed understanding of the charging behavior and thermodynamics of the electrochemical interface. Experiments can independently probe the overall charge response of the electrochemical…
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…
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 reactions involve the movement of charges, and this work presents a mathematical model for describing chemical reactions in electrolytes. The model is developed using an energy variational method that aligns with classical…
Proton-coupled electron transfers (PCET) are elementary steps in electrocatalysis. However, accurate calculations of PCET rates remain challenging, especially considering nuclear quantum effects (NQEs) under a constant potential condition.…
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…
Porous electrodes are widely used in electrochemical systems, where accurately determining electric potentials, particularly overpotentials, is essential for understanding electrode behavior. At the macroscopic scale, porous electrodes are…
Artifacts arise in the simulations of electrolytes using periodic boundary conditions (PBC). We show the origin of these artifacts are the periodic image charges and the constraint of charge neutrality inside the simulation box, both of…
The continuum-scale electrokinetic porous-media flow and excess charge redistribution equations are uncoupled using eigenvalue decomposition. The uncoupling results in a pair of independent diffusion equations for "intermediate" potentials…
Charge-transfer excited states are highly relevant for applications in molecular electronics. However, the accurate calculation of these states in large systems is challenging since wave function methods are prohibitively expensive,…
We present an improved field-theoretic approach to the grand-canonical potential suitable for linear scaling molecular dynamics simulations using forces from self-consistent electronic structure calculations. It is based on an exact…
Studies on nanoscale materials merit careful development of an electrostatics model concerning discrete point charges within dielectrics. The discrete charge dielectric model treats three unique interaction types derived from an external…
Simulating electrochemical interfaces using density functional theory (DFT) requires incorporating the effects of electrochemical potential. The electrochemical potential acts as a new degree of freedom that can effectively tune DFT results…