Electrochemical Modulation of Photoelectric Emission Thresholds in Organic Electrolytes

https://doi.org/10.65161/recu3e1vNHKbAzNue

The photoelectric effect, foundational to quantum mechanics, has been predominantly characterized in vacuum environments for over a century, with emission thresholds considered intrinsic material properties. This theoretical study explores how electrochemical interfaces modify these thresholds in organic electrolytes. We develop a comprehensive energy balance framework incorporating interfacial electrochemistry, electron solvation physics, and charge screening effects. Calculations indicate that noble metals—gold, palladium, and iridium—with work functions (5.10-5.27 eV) prohibiting electron emission under 4.87 eV photons in vacuum,should enable emission in low-polarity organic solvents. Applied electrode potentials modulate effective work functions by 0.73-1.00 eV through interfacial potential control, while solvent selection minimizes solvation losses (0.05-0.40 eV in organics vs 1.7 eV in water). We predict measurable photocurrents (0.205 μA/cm²) and positive kinetic energies (up to 0.439 eV) across five organic solvent systems, identifying toluene as the optimal medium. This framework extends photoelectric principles to electrochemical interfaces and provides testable predictions for voltage-dependent electron emission.