Insights into electron tunneling and confinement effects in electrochemical double layers using the jellium model

Understanding electronic behavior within the electrochemical double layer (EDL) is essential in electrochemistry due to its pivotal role in influencing the performance of electrochemical devices and enabling various applications. This study integrates the EDL potential energy into the Kohn–Sham potential within a jellium model, usually encompassing exchange–correlation, Hartree, and ionic background potentials. By employing this approach, the electron density distributions and wavefunctions in response to varying electrode potentials are explored. The findings reveal voltage-dependent confinement effects and electron localization within the EDL, offering deeper insights into electron dynamics at electrochemical interfaces and informing the design of advanced electrochemical systems and theoretical frameworks.