Issue 26, 2019

Solvent reorganization triggers photo-induced solvated electron generation in phenol

Abstract

The analysis of the absorption spectrum and density of states of a cluster of phenol solvated with 15 water molecules indicates that the reorganization of the water molecules, facilitating the formation of solvated electrons, is a plausible mechanism in the photodissociation of phenol. Using quantitative wavefunction analysis, we demonstrate that while charge-transfer states involving electron transfer from phenol to water are mainly dark, a considerable number of them exists below the maximum of the ππ* absorption band and could be populated by internal conversion. These low-lying charge-transfer states do not show extended O–H distances, but are found for large electron–hole separations at which several water molecules can solvate and stabilize the transferred electron. Thus, charge-transfer states in solvated phenol can be stabilized by two factors: (i) elongation of the O–H bond, as was extensively discussed in the past, and (ii) reorganization of solvent molecules, as it is shown here.

Graphical abstract: Solvent reorganization triggers photo-induced solvated electron generation in phenol

Supplementary files

Article information

Article type
Paper
Submitted
26 Oct 2018
Accepted
10 Dec 2018
First published
10 Dec 2018
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2019,21, 14261-14269

Solvent reorganization triggers photo-induced solvated electron generation in phenol

I. Sandler, J. J. Nogueira and L. González, Phys. Chem. Chem. Phys., 2019, 21, 14261 DOI: 10.1039/C8CP06656F

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