Vibration Coupling Effects Mediated Interference in Phonon–Electron Energy Transfer

ABSTRACT This work elucidates the lattice dynamical origins of enhanced adsorbate–substrate interactions in oxygen‐deficient Co 3 O 4 via first‐principles calculations. We reveal that oxygen vacancy formation induces a localized reconstruction of the phonon landscape, characterized by the emergence of high‐frequency vibrational modes specifically on atoms neighboring the defect. Critically, these defect‐induced modes exhibit strong spectral resonance with the vibrational centers of H 2 O molecules, thereby governing the thermodynamic favorability of adsorption through a vibrational coupling mechanism. By establishing a direct correlation between local phonon redistribution and chemical reactivity, this study provides a theoretical basis for leveraging phonon engineering in the design of advanced electrode materials for energy storage applications.