Electronic dynamics in liquids are of fundamental importance, but time-resolved experiments have so far remained limited to the femtosecond time scale. We report the extension of attosecond spectroscopy to the liquid phase. We measured time delays of 50 to 70 attoseconds between the photoemission from liquid water and that from gaseous water at photon energies of 21.7 to 31.0 electron volts. These photoemission delays can be decomposed into a photoionization delay sensitive to the local environment and a delay originating from electron transport. In our experiments, the latter contribution is shown to be negligible. By referencing liquid water to gaseous water, we isolated the effect of solvation on the attosecond photoionization dynamics of water molecules. Our methods define an approach to separating bound and unbound electron dynamics from the structural response of the solvent.
Time-resolved observation of the Eigen cation in liquid water