Theoretical investigation of vibrational energy transfer of water at the gas/liquid interface around 3400 cm−1

Abstract

Using molecular dynamics simulations based on neural network potentials and a mixed quantum/classical approach, we theoretically explore vibrational energy transfer pathways for OH groups around 3400 cm−1 at interfaces. Our calculations show that intramolecular vibrational energy transfer has a time constant of 369.2 fs, aligning with experimental findings. The reorientation time is 1624 fs. The intermolecular vibrational energy transfer rate is slower due to weak couplings between water molecules. Our results suggest that intramolecular energy transfer is the main driver of vibrational energy transfer for OH groups around 3400 cm−1 at the gas/water interface.