Photooxidation of the Phenolate Anion is Accelerated at the Water/Air Interface.

Molecular photodynamics can be dramatically affected at the water/air interface. Probing such dynamics is challenging, with product formation often probed indirectly through its interaction with interfacial water molecules using time-resolved and phase-sensitive vibrational sum-frequency generation (SFG). Here, the photoproduct formation of the phenolate anion at the water/air interface is probed directly using time-resolved electronic SFG and compared to transient absorption spectra in bulk water. The mechanisms are broadly similar, but 2 to 4 times faster at the surface. An additional decay is observed at the surface which can be assigned to either diffusion of hydrated electrons from the surface into the bulk or due to increased geminate recombination at the surface. These overall results are in stark contrast to phenol, where dynamics were observed to be 10 times faster and for which the hydrated electron was also a photoproduct. Our attempt to probe phenol showed no electron signal at the interface.