Theory of vibrational Stark effect for adsorbates and diatomic molecules

TL;DR

This paper revisits the vibrational Stark effect at electrochemical interfaces, quantifying quantum contributions and revealing that anharmonicity influences the effect, which can explain experimental nonlinearities.

Contribution

It provides a quantum perturbation theory analysis of VSE, highlighting the role of anharmonicity and challenging the classical Lambert theory assumptions.

Findings

Quantum effect on VSE is 2-3% for CO and 8-10% for adsorbed hydrogen.

Anharmonic coefficient $$ determines the quantum contribution to VSE.

Nonlinear VSE slope arises from the nonlinear electric field-potential relation.

Abstract

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-principle calculations for this issue. Here we revisit this problem by addressing the fundamental question that 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, $\eta$, and show that for CO, $\eta \sim $ 2 - 3\%, while for adsorbed hydrogen on Pt electrode, $\eta \sim$ 8 - 10\%, using the experimental data. We find that $\eta$ is determined by the anharmonic coefficient $\chi_e$. Without 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 long-standing controversial in experiments.