Real-time tracking of the intramolecular vibrational dynamics of liquid water

Water’s polarity and hydrogen-bond network give rise to its unique chemical and biochemical behaviour. Its vibrational motions, occurring on a few-femtosecond timescale, govern ultrafast energy transfer within the hydrogen-bond network. However, direct real-time observation of these motions has remained elusive due to the extreme temporal resolution required. Here, we investigate the ground-state vibrational dynamics of liquid water initiated by a sub-5 fs near-infrared (NIR) pump pulse via Impulsive Stimulated Raman Scattering (ISRS). Using few-fs ultraviolet (UV) probe pulses transmitted through a 5 µm-thick liquid jet, we monitor the coherent vibrational wave packet dominated by the OH stretch mode, exhibiting a 10 fs oscillation period and a 25 fs damping time. These results reveal the rapid dephasing of the OH stretch mode preceding its relaxation through coupling to the bending vibrations, highlighting the importance of intermolecular couplings of liquid water in the high frequency vibrational dynamics.