Evaluating continuum solvation models for the electrode-electrolyte interface: Challenges and strategies for...

Area of Science:

• Computational chemistry
• Electrochemistry
• Materials science

Background:

• Ab initio modeling is crucial for predicting electrochemical behavior.
• Accurate computational electrochemical methods require careful benchmarking.
• Existing continuum models, parameterized for molecular solvation, may not accurately represent metal surfaces.

Purpose of the Study:

• To evaluate the accuracy of continuum models for metal surfaces in electrochemical systems.
• To identify limitations of current models in capturing electrolyte-interface interactions.
• To develop improved solvation models for accurate electrochemical calculations.

Main Methods:

• Utilizing charging curves of an electrode with an inert aqueous electrolyte.
• Analyzing the performance of continuum solvation models.
• Reparameterizing popular solvation models using experimental surface charge data for Ag(100).

Main Results:

• Most continuum models undersolvate metal surfaces and underestimate surface charge.
• Models fail to capture key electrolyte-interface features relevant to metal surfaces.
• Reparameterized models show improved accuracy for metal surfaces.

Conclusions:

• Current continuum models require adjustments for reliable electrochemical simulations of metal surfaces.
• Reparameterization enhances model utility for metal surfaces while retaining molecular solvation capabilities.
• This work provides a pathway for more accurate ab initio electrochemical modeling.