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Primary Photochemical Processes of Excited Phenols in Ethanol†

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The primary photochemical processes of phenols in ethanol solution are studied by nanosecond laser flash photolysis. Transient signals in photolysis at 266 nm are recognized as belonging to solvated electrons, phenoxyl radicals, and the triplet state of the phenol. The onset of the T-T absorption spectrum of phenol is around 450nm. In addition to the absorption around 400 nm, phenoxyl radicals were found to exhibit a broad, weak absorption band in the red region where the extinction coefficient is determined to be 300 ±150 M-1 cm-1 at 580 nm. A delayed fluorescence of phenol, assigned to T-T annihilation, is observed in the region 310-360 nm. Laser dose dependent decay kinetics of solvated electrons is explained by their reaction with the triplet state of the phenol. Simple model calculations show that the rate constant of this latter reaction is approximately 102 times larger than that for reaction with the corresponding ground-state phenol.

Affiliations: 1: Research Center for Advanced Science and Technology, the University of Tokyo, 4-6-1 Komaba, Meguro, Tokyo, JAPAN; 2: Radiation Laboratory and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556-0579, USA


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