Adaptive Electric Fields Embedded Electrochemical Barrier Calculations.

Area of Science:

• Computational chemistry
• Physical chemistry
• Materials science

Background:

• Electrochemical interfaces are complex systems with variable electron numbers.
• Standard first-principles simulations struggle with fixed electron counts.
• Simulating grand canonical ensembles of electrons is computationally challenging.

Purpose of the Study:

• To develop a novel constant potential simulation method for electrochemical interfaces.
• To enable accurate first-principles simulations of systems with varying electron numbers.
• To ensure model independence in electrochemical simulations.

Main Methods:

• Developed a constant potential simulation method by adding an adaptive electric field.
• Utilized a charge-neutral system with electric field as the controlling variable.
• Defined an internal reversible hydrogen electrode potential (ϕIRHE) for model independence.

Main Results:

• Validated the method by calculating reaction energies for electrochemical reactions.
• Achieved results comparable to the computational hydrogen electrode model and experimental data.
• Analyzed transition state structures and charge transfer coefficients on Ag(111) surface.

Conclusions:

• The developed constant potential method accurately simulates electrochemical interfaces.
• The method provides model-independent results, enhancing simulation reliability.
• This approach advances the computational study of electrochemical reactions and surface phenomena.