Physikalische Chemie - Direktor: Prof. Dr. Martin Wolf
Department Seminar
Host: K. Campen

Wednesday, January 23, 2019, 11:00 am
PC Seminar Room, G 2.06, Faradayweg 4
Prof. Dr. Eric Borguet
Department of Chemistry, Temple University, Philadelphia PA
The impact of ions on ultrafast vibrational spectroscopy and dynamics at aqueous interfaces
Interfacial water structure is key to many chemical and physical processes. It can be probed by vibrational sum-frequency generation (vSFG) spectroscopy as well as ultrafast time-resolved vSFG. However, a more complete microscopic understanding requires additional techniques such as molecular dynamics simulations. Our experiments show that in the absence of surface charge (pH 2), water at silica surfaces exhibits significantly slower OH stretch vibrational relaxation (~600 fs) compared to bulk water. However, at charged silica surfaces (e.g., pH 6), bulk-like fast dynamics (~200 fs) are observed at low ionic strength. This decelerates to ~600 fs with the addition of NaCl. In parallel, vSFG results demonstrated that silica interfacial water structure is most sensitive to ions at pH=6-8, correlating with the known salt and pH dependence of silica surface reactivity. Consequently, it is unclear whether the observed slowing of the vibrational dynamics is due to the reduction in the Debye length, or because of changes in the local hydrogen bonding environment caused by the electrolyte and how this might depend on the identity of the ions or the solid surface. The combination of molecular dynamics simulations with spectroscopic and time-resolved vSFG experiments on aqueous Al2O3 interfaces sheds light on the ongoing debate on the role of ions in interfacial water structure and whether the observed behavior is specific to silica/water interfaces or can be generalized to other aqueous interfaces.