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Solvatation de l'électron dans des solutions aqueuses et dans des alcools : étude par spectroscopie d'absorption femtoseconde

Abstract : In this work we studied, with a time-resolved femtosecond pump-probe spectroscopy method, the influence of the environment on the optical absorption spectrum of the solvated electron. First, we studied the absorption spectrum of the solvated electron in concentrated aqueous solutions of salts. Reviewing ten cations and two counterion, we observed a continuous shift of the absorption band toward shorter wavelengths without any change in shape and the bandwidth. The spectral shift depends on the characteristics of the cation (size and charge) but also on the counterion (screening effect and salt dissociation). Then, we studied the electron solvation dynamics in several alcohols (propane-1-ol, pentane-1-ol, propane-1,2-diol, propane-1,3-diol and glycerol). The transient absorption spectra recorded on 450 ps and between 440 and 710 nm have showed that, after its formation, the solvated electron mainly absorbs in the near-IR, then its spectrum evolves toward the visible domain to reach the spectrum of the stable species after a few tens of picoseconds. Global analysis of these data by two solvation models (stepwise and continuous) using a powerful Bayesian inference method coupled with a Markov Chain Monte Carlo method has allowed us to obtain characteristic times that correlate the macroscopic properties of the liquids (viscosity and dielectric relaxation times).
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https://tel.archives-ouvertes.fr/tel-00010713
Contributor : Julien Bonin <>
Submitted on : Friday, October 21, 2005 - 5:24:15 PM
Last modification on : Saturday, April 20, 2019 - 1:23:46 AM
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Julien Bonin. Solvatation de l'électron dans des solutions aqueuses et dans des alcools : étude par spectroscopie d'absorption femtoseconde. Autre. Université Paris Sud - Paris XI, 2005. Français. ⟨tel-00010713⟩

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