Practical Considerations for Continuum Models Applied to Surface Electrochemistry.

Area of Science:

• Computational Chemistry
• Surface Science
• Electrochemistry

Background:

• Accurate modeling of electrolytes at electrochemical interfaces is crucial for ab initio simulations of charge transfer.
• Hybrid polarizable continuum models (PCMs)/ab initio models offer computational efficiency for solvation and electrolyte charge.
• Existing PCM/ab initio methods face challenges with large cell heights for convergence and iterative tuning for constant potential.

Purpose of the Study:

• To present a simple capacitor model to address computational challenges in PCM/ab initio simulations of surface electrochemistry.
• To develop methods for energy correction at finite cell heights and facile mapping of reaction energetics.
• To reduce the computational overhead for applying PCMs to surface electrochemistry.

Main Methods:

• Development of a simple capacitor model for the electrochemical interface.
• Derivation of an energy correction for finite cell heights to approximate large cell energies.
• Demonstration of mapping reaction energetics from constant charge to constant potential conditions.

Main Results:

• A method to obtain large cell energies without additional computational cost was derived.
• Reaction energetics at constant potential can be easily determined from constant charge calculations, eliminating iterative schemes.
• The proposed methods reduce computational overhead by over an order of magnitude.

Conclusions:

• The capacitor model effectively circumvents challenges associated with large cell heights and potential tuning in PCM/ab initio simulations.
• This work significantly enhances the computational efficiency of applying polarizable continuum models to surface electrochemistry.
• The developed approach paves the way for more accessible and cost-effective ab initio simulations of electrochemical processes.