%0 Journal Article %T Oxidation of bromide ions by hydroxyl radicals: Spectral characterization of the intermediate BrOH•- %+ Laboratoire de Chimie Physique D'Orsay (LCPO) %A Lampre, Isabelle %A Marignier, Jean-Louis %A Mirdamadi-Esfahani, Malaknaz %A Pernot, Pascal %A Archirel, Pierre %A Mostafavi, Mehran %< avec comité de lecture %@ 1089-5639 %J Journal of Physical Chemistry A %I American Chemical Society %8 2013 %D 2013 %R 10.1021/jp310759u %K water %K reactivity %K reduction %K electrons %K hydroxyl radicals %K spectral domains %K quantum chemical calculations %K bayesian data analysis %K transition energy %K spectral characterization %K extinction coefficients %K number of degrees of freedom %K picosecond pulse radiolysis %K intermediate specie %K bromide ions %K solvation dynamics %K aqueous-solutions %K pulse-radiolysis %K 2-photon ionization %K liquid polyols %K earth alkaline-metals %Z Chemical SciencesJournal articles %X The reaction of •OH with Br- has been reinvestigated by picosecond pulse radiolysis combined with streak camera absorption detection and the obtained spectro-kinetics data have been globally analyzed using Bayesian data analysis. For the first time, the absorption spectrum of the intermediate species BrOH•- has been determined. This species absorbs in the same spectral domain as Br2 •-: the band maximum is roughly at the same wavelength (λmax = 352 nm instead of 354 nm) but the extinction coefficient is smaller (εmax = 7800 ± 400 dm3 mol-1 cm-1 compared with 9600 ± 300 dm3 mol-1 cm-1) and the band is broader (88 nm versus 76 nm). Quantum chemical calculations have also been performed and corroborate the experimental results. In contrast to Br2•-, the existence of several water-BrOH•- configurations leading to different transition energies may account for the broadening of the absorption spectrum in addition to the higher number of degrees of freedom. © 2013 American Chemical Society. %G English %2 https://universite-paris-saclay.hal.science/hal-04037324/document %2 https://universite-paris-saclay.hal.science/hal-04037324/file/DOC.pdf %L hal-04037324 %U https://universite-paris-saclay.hal.science/hal-04037324 %~ CNRS %~ UNIV-PSUD %~ INC-CNRS %~ UNIV-PARIS-SACLAY %~ UNIV-PSUD-SACLAY %~ ICPO