Oxidation of bromide ions by hydroxyl radicals: Spectral characterization of the intermediate BrOH<sup>•-</sup> - Université Paris-Saclay Access content directly
Journal Articles Journal of Physical Chemistry A Year : 2013

Oxidation of bromide ions by hydroxyl radicals: Spectral characterization of the intermediate BrOH•-

Abstract

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.
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Dates and versions

hal-04037324 , version 1 (20-03-2023)

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Isabelle Lampre, Jean-Louis Marignier, Malaknaz Mirdamadi-Esfahani, Pascal Pernot, Pierre Archirel, et al.. Oxidation of bromide ions by hydroxyl radicals: Spectral characterization of the intermediate BrOH•-. Journal of Physical Chemistry A, 2013, ⟨10.1021/jp310759u⟩. ⟨hal-04037324⟩
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