Exploring Autoionization and Photoinduced Proton-Coupled Electron Transfer Pathways of Phenol in Aqueous Solution

• DOI: 10.1021/acs.jpclett.5b01861
• Publication Date: 2015-09-30T22:42:33Z
• Authors: Thomas A. A. Oliver; Yuyuan Zhang; Anirban Roy; Michael N. R. Ash...; Stephen E. Bradforth
• Keywords: Ions; UV photochemistry; proton transfer; Phenol; solvated electrons; Water; Electrons; 540; electron transfer; 530; 01 natural sciences; Electron Transport; nonradiative decay; 0103 physical sciences; Deuterium Oxide; Protons

The excited state dynamics of phenol in water have been investigated using transient absorption spectroscopy. Solvated electrons and vibrationally cold phenoxyl radicals are observed upon 200 and 267 nm excitation, but with formation time scales that differ by more than 4 orders of magnitude. The impact of these findings is assessed in terms of the relative importance of autoionization versus proton-coupled electron transfer mechanisms in this computationally tractable model system.