A polarizable molecular dynamics method for electrode-electrolyte interfacial electron transfer under the constant...

Area of Science:

• Physical Chemistry
• Computational Electrochemistry
• Materials Science

Background:

• Electron transfer (ET) at electrode-electrolyte interfaces is fundamental to electrochemistry.
• Computational simulations are vital for understanding interfacial dynamics and reaction energetics.
• Accurate simulations require knowledge of electron chemical potentials and interfacial response to voltage.

Purpose of the Study:

• To develop a classical fully polarizable molecular dynamics method for non-adiabatic ET processes.
• To investigate the influence of electronic polarization of metal electrodes and solvent molecules on interfacial structure and ET energetics.
• To analyze the role of electronic polarization in Marcus free energy curves.

Main Methods:

• Developed a classical fully polarizable molecular dynamics (MD) approach.
• Incorporated electronic polarizability for both metal electrodes and solvent molecules.
• Introduced electron chemical potentials based on the chemical potential equalization principle, with their difference set by the applied voltage.

Main Results:

• The electronic polarization of solvent molecules significantly affects interfacial structure and Marcus free energy curves.
• Solvent polarization is crucial for accurate calculation of reorganization energies.
• The influence of solvent polarization diminishes as redox species approach the electrode, where metal electrode polarization becomes dominant.

Conclusions:

• The developed MD method accurately captures non-adiabatic interfacial ET processes.
• Electronic polarization of both solvent and electrode is essential for precise electrochemical simulations.
• Understanding these polarization effects is key to controlling and optimizing electrochemical reactions.