Vibrational energy transfer of water at interfaces mediated by Fermi resonance

Abstract

Combining neural network-based molecular dynamics simulations with the mixed quantum/classical approach, we elucidate the vibrational energy transfer pathways of interfacial OH groups (3115–3285 cm−1). This study reveals that intermolecular transfer exhibits the slowest kinetics due to the attenuated dipole–dipole coupling at interfaces, while reorientation, intramolecular, and Fermi-resonant pathways proceed faster. Notably, Fermi resonance largely influences the observed energy transfer dynamics. The overall time is in agreement with experimental measurements. These findings establish Fermi resonance as a critical factor in the vibrational energy transfer near 3200 cm−1 at the gas/water interface.