Aqueous Solvation Dynamics at Metal Oxide Surfaces

Broadband transient absorption (TA) spectroscopy, three-pulse photon echo peak shift (3PEPS), and anisotropy decay measurements were used to study the solvation dynamics in bulk water and interfacial water at ZrO2 surfaces, using Eosin Y as a probe. The 3PEPS results show a multiexponential behavior with two subpicosecond components that are similar in bulk and interfacial water, while a third component of several picoseconds is significantly lengthened at the interface. The bandwidth correlation function from TA spectra exhibits the same behavior, and the TA spectra are well reproduced using the doorway-window picture with the time constants from PEPS. Our results suggest that interfacial water is restricted to a thickness of less than 5 angstrom. Also the high-frequency collective dynamics of water does not seem to be affected by the interface. On the other hand, the increase of the third component may point to a slowing down of diffusional motion at the interface, although other effects, may play a role, which are discussed.