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Real-time observation of the photoionization-induced water rearrangement dynamics in the 5-hydroxyindole–water cluster by time-resolved IR spectroscopy

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Abstract

Solvation plays an essential role in controlling the mechanism and dynamics of chemical reactions in solution. The present study reveals that changes in the local solute–solvent interaction have a great impact on the timescale of solvent rearrangement dynamics. Time-resolved IR spectroscopy has been applied to a hydration rearrangement reaction in the monohydrated 5-hydroxyindole–water cluster induced by photoionization of the solute molecule. The water molecule changes the stable hydration site from the indolic NH site to the substituent OH site, both of which provide a strongly attractive potential for hydration. The rearrangement time constant amounts to 8 ± 2 ns, and is further slowed down by a factor of more than five at lower excess energy. These rearrangement times are slower by about three orders of magnitude than those reported for related systems where the water molecule is repelled from a repulsive part of the interaction potential toward an attractive well. The excess energy dependence of the time constant is well reproduced by RRKM theory. Differences in the reaction mechanism are discussed on the basis of energy relaxation dynamics.

Graphical abstract: Real-time observation of the photoionization-induced water rearrangement dynamics in the 5-hydroxyindole–water cluster by time-resolved IR spectroscopy

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Publication details

The article was received on 08 Sep 2017, accepted on 25 Oct 2017 and first published on 27 Oct 2017


Article type: Paper
DOI: 10.1039/C7CP06127G
Citation: Phys. Chem. Chem. Phys., 2017, Advance Article
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    Real-time observation of the photoionization-induced water rearrangement dynamics in the 5-hydroxyindole–water cluster by time-resolved IR spectroscopy

    M. Miyazaki, A. Naito, T. Ikeda, J. Klyne, K. Sakota, H. Sekiya, O. Dopfer and M. Fujii, Phys. Chem. Chem. Phys., 2017, Advance Article , DOI: 10.1039/C7CP06127G

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