Probing the Dynamics of Solvation and Structure of the OH- Ion in Aqueous Solution from Picosecond Transient Absorption Measurements 英文参考文献.docVIP

Molecules 2010, 15, 3366-3377; doi:10.3390/moleculeOPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Article Probing the Dynamics of Solvation and Structure of the OH- Ion in Aqueous Solution from Picosecond Transient Absorption Measurements Olivier Poizat * and Guy Buntinx 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), Bat. C5, Université des Sciences et Technologies de Lille, 59655 Villeneuve dAscq, France; E-Mail: guy.buntinx@univ-lille1.fr (G.B.) ? Author to whom correspondence should be addressed; E-Mail: olivier.poizat@univ-lille1.fr; Tel.: +33 (0)3 20 43 40 85; Fax: +33 (0)3 20 43 67 55. Received: 24 March 2010; in revised form: 16 April 2010 / Accepted: 6 May 2010 / Published: 7 May 2010 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-diazabicyclo[2.2.2]octane (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-(H2O)3 is formed first before evolving toward a final four-water hydration structure OH-(H2O)4. Keywords: transient absorption spectroscopy; hydroxide ion solvation; solvation dynamics; bipyridine  Molecules 2010, 15 3367 1. Introduction The nature and transport mechanism of the proton (H+) and hydroxide ion (OH-) in aqueous solution play a determinant role in a lot of areas related to acid-base