Wavelength dependent mechanism of phenolate photooxidation in aqueous solution.

Phenolate photooxidation is integral to a range of biological processes, yet the mechanism of electron ejection has been disputed. Here, we combine femtosecond transient absorption spectroscopy, liquid-microjet photoelectron spectroscopy and high-level quantum chemistry calculations to investigate the photooxidation dynamics of aqueous phenolate following excitation at a range of wavelengths, from the onset of the S 0 -S 1 absorption band to the peak of the S 0 -S 2 band. We find that for λ ≥ 266 nm, electron ejection occurs from the S 1 state into the continuum associated with the contact pair in which the PhO˙ radical is in its ground electronic state. In contrast, we find that for λ ≤ 257 nm, electron ejection also occurs into continua associated with contact pairs containing electronically excited PhO˙ radicals and that these contact pairs have faster recombination times than those containing PhO˙ radicals in their ground electronic state.