On the mechanism of phenolate photo-oxidation in aqueous solution.
作者： Alexandra L. Tyson , Jan R. R. Verlet
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摘要: The photo-oxidation dynamics following ultraviolet (257 nm) excitation of the phenolate anion in aqueous solution is studied using broadband (550–950 transient absorption spectroscopy. A clear signature from electron ejection observed on a sub-picosecond timescale, followed by cooling and decay signal to constant offset that assigned hydrated electron. are compared charge-transfer-to-solvent iodide at same wavelength shown be very similar these. This stark contrast previous study excited 266 nm, which emission was over longer timescales. We account for differences simple Marcus picture tunneling rate depends sensitively initial energy. After emission, contact pair formed undergoes geminate recombination dissociation form free rates slightly faster than those system. Our results show that, although underlying chemical physics differs between phenolate, can appear similar.
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