Picosecond mass-selective measurements of phenol-(NH3)n acid–base chemistry in clusters

Abstract

The rate of proton transfer from the acidic S1 state of phenol to the basis solvent (NH3)n was measured as a function of solvent cluster size n. A distinct reaction threshold was observed for solvent size n=5 for 266 nm picosecond excitation. The proton transfer rate was measured to be ka=(60±10 ps)−1 for n=5–7. A competitive recombination rate of k−a =(350±100 ps)−1 occurs for n=5. Additional solvation stabilizes the product side causing the reaction enthalpy and consequently k−a to decrease. No evidence of proton transfer was observed when phenol was seeded in the less basic solvent clusters (CH3OH)n and (H2O)n.