Robertson, K;
Fortune, WG;
Davies, JA;
Boichenko, A;
Scholz, MS;
Tau, O;
Bochenkova, AV;
(2023)
Wavelength dependent mechanism of phenolate photooxidation in aqueous solution.
Chemical Science
10.1039/d3sc00016h.
(In press).
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Abstract
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 S0-S1 absorption band to the peak of the S0-S2 band. We find that for λ ≥ 266 nm, electron ejection occurs from the S1 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.
| Type: | Article |
|---|---|
| Title: | Wavelength dependent mechanism of phenolate photooxidation in aqueous solution |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1039/d3sc00016h |
| Publisher version: | https://doi.org/10.1039/D3SC00016H |
| Language: | English |
| Additional information: | This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry |
| URI: | https://discovery-pp.ucl.ac.uk/id/eprint/10167066 |
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