Nowadays the vibrational Stark effect (VSE) of adsorbates at the electrochemical interfaces is generally investigated using the Lambert theory, in which the strong electric field across the interfaces can be treated as some kind of perturbation. Lambert found that the VSE arises mainly from the classical effect, and the quantum effect is negligible. This idea is accepted by almost all current first-principles calculations for this issue. Here we revisit this problem by addressing the fundamental question of to what extent the quantum effect is important for VSE, and if it is observable, then which physical quantity determines this effect. We use the Morse, Lennard-Jones, and Dunham potentials as basic potentials to explore this problem using quantum perturbation theory. We define the relative difference between quantum and classical VSE slopes to define the quantum effect, yielding $\eta \sim 7\hslash \omega /12D_e$, where $\hslash$, $\omega$, and $D_e$ are the Planck constant, vibrational frequency, and binding energy, respectively. With this formula we show that for CO, $\eta \sim 2–3$%, while for adsorbed hydrogen on Pt electrode, $\eta \sim$ 8–10%, using the experimental measurable data. We find that $\eta$ is directly determined by the anharmonic coefficient ${\chi }_e$. With these results we present a new understanding of the VSE as a function of electric field and potential in electrochemical experiments, showing that the nonlinear slope of VSE as a function of potential should arise from the nonlinear relation between electric field and potential across the interfaces, which may resolve the longstanding controversial in experiments.

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• Adsorption
• Chemical Physics & Physical Chemistry
• Vibrational states
• Molecules
• Perturbative methods
• Schroedinger equation