Probing the Dynamics of Solvation and Structure of the OH- Ion in Aqueous Solution from Picosecond Transient Absorption MeasurementsReport as inadecuate




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Laboratoire de Spectrochimie Infrarouge et Raman UMR 8516 de l’Université et du CNRS, Centre dEtudes et de Recherches Lasers et Applications FR 2416 du CNRS, Bât. C5, Université des Sciences et Technologies de Lille, 59655 Villeneuve dAscq, France





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Abstract The reaction of intracomplex proton transfer 44BPY-



HO-H ® 44BPYH. + OH- that follows the photoreduction of 4,4’-bipyridine 44BPY into its anion radical 44BPY- in the presence of 1,4-diazabicyclo2.2.2octane DABCO is investigated in acetonitrile-water mixtures by using picosecond transient absorption. The dependence of the appearance kinetics of the 44BPYH. radical on the water content reveals a highly diffusional proton transfer process that is controlled by the dynamics of solvation of the released hydroxide ion. The results are interpreted on the basis of a two-step mechanism where an intermediate solvation complex 44BPYH.OH-H2O3 is formed first before evolving toward a final four-water hydration structure OH-H2O4.

Keywords: transient absorption spectroscopy; hydroxide ion solvation; solvation dynamics; bipyridine transient absorption spectroscopy; hydroxide ion solvation; solvation dynamics; bipyridine





Author: Olivier Poizat * and Guy Buntinx

Source: http://mdpi.com/



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