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Issue 26, 2014
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Competition between excited state proton and OH transport via a short water wire: solvent effects open the gate

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Abstract

We investigate the acid–base proton exchange reaction in a microsolvated bifunctional chromophore by means of quantum chemical calculations. The UV/vis spectroscopy shows that equilibrium of the keto- and enol-forms in the electronic ground state is shifted to the keto conformation in the excited state. A previously unknown mechanism involving a hydroxide ion transport along a short water wire is characterized energetically, which turns out to be competitive with the commonly assumed proton transport. Both mechanisms are shown to have a concerted character, as opposed to a step-wise mechanism. The alternative mechanism of a hydrogen atom transport is critically examined, and evidence for strong solvent dependence is presented. Specifically, we observe electrostatic destabilization of the corresponding πσ* state by the aqueous solvent. As a consequence, no conical intersections are found along the reaction pathway.

Graphical abstract: Competition between excited state proton and OH− transport via a short water wire: solvent effects open the gate

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Publication details

The article was received on 06 Mar 2014, accepted on 11 Apr 2014 and first published on 16 Apr 2014


Article type: Communication
DOI: 10.1039/C4CP00970C
Citation: Phys. Chem. Chem. Phys., 2014,16, 13047-13051
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    Competition between excited state proton and OH transport via a short water wire: solvent effects open the gate

    G. Bekçioğlu, C. Allolio, M. Ekimova, E. T. J. Nibbering and D. Sebastiani, Phys. Chem. Chem. Phys., 2014, 16, 13047
    DOI: 10.1039/C4CP00970C

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