Electric fields control chemical reactivity in a wide range of systems, including enzymes and electrochemical interfaces. Characterizing the electric fields at electrode-solution interfaces is critical for understanding heterogeneous catalysis and associated energy conversion processes. To address this challenge, recent experiments have probed the response of the nitrile stretching frequency of 4-mercaptobenzonitrile (4-MBN) attached to a gold electrode to changes in the solvent and applied electrode potential. Herein, this system is modeled with periodic density functional theory using a multilayer dielectric continuum treatment of the solvent and at constant applied potentials. The impact of the solvent dielectric constant and the applied electrode potential on the nitrile stretching frequency computed with a grid-based method is in qualitative agreement with the experimental data. In addition, the interfacial electrostatic potentials and electric fields as a function of applied potential were calculated directly with density functional theory. Substantial spatial inhomogeneity of the interfacial electric fields was observed, including oscillations in the region of the molecular probe attached to the electrode. These simulations highlight the microscopic inhomogeneity of the electric fields and the role of molecular polarizability at electrode-solution interfaces, thereby demonstrating the limitations of mean-field models and providing insights relevant to the interpretation of vibrational Stark effect experiments.
