High energy radiation femtochemistry of water molecules: early electron-radical pairs processes

Abstract : The damages triggered by ionizing radiation on chemical and biological targets depend on the survival probability of radicals produced in clusters of ionization-excitation events. In this paper, we report on femtolysis (FEMTOsecond radioLYSIS) of pure liquid water using an innovative laser produced high-energy, ultra-short electron bunches in the 2.5-15 MeV range and high energy radiation femtochemistry (HERF) measurements. The short-time monitoring of a primary reducing radical, hydrated electron e¯¯aq, has been performed in confined ionization spaces (nascent spurs). The calculated yield of hydrated electrons at early time,G(e⁻aq)ET , is estimated to be 6.5 ± 0.5 (number/100 eV) at t ~ 5 ps after the ultrafast energy deposition. This estimated value is high compare to (i) the available data of previous works that used scavenging techniques; (ii) the predictions of stochastic water radiolysis modelling for which the initial behaviour of hydrated electron is investigated in the framework of a classical diffusion regime of independent pairs. The HERF developments give new insights into the early ubiquitous radical escape probability in nascent aqueous spurs and emphasize the importance of short-lived solvent bridged electron-radical complexes [H3O+...e⁻aq..OH]nH2O (non-independent pairs). A complete understanding of the G(e⁻aq)ET value needs to account for quantum aspects of 1s-like trapped electron ground state and neoformed prototropic radicals that govern ultra-fast recombination processes within these non-independent pair configurations. Femtolysis data emphasize that within a time-dependent non-diffusion regime, spatio-temporal correlations between hydrated electron and nearest neighbours OH radical or hydrated proton (H3O+) would assist ultrafast anisotropic 1D recombination within solvent bridged electron-radical complexes. The emerging HERF domain would provide guidance for understanding of ultrashort-lived sub-structure of tracks and stimulate future semi-quantum simulations on prethermal radical reactions.
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Submitted on : Wednesday, March 9, 2011 - 6:10:16 PM
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Yann Gauduel, Yannick Glinec, Jean-Philippe Rousseau, Frédéric Burgy, Victor Malka. High energy radiation femtochemistry of water molecules: early electron-radical pairs processes. The European Physical Journal D : Atomic, molecular, optical and plasma physics, EDP Sciences, 2010, 60 (1), pp.121 - 135. ⟨10.1140/epjd/e2010-00152-2⟩. ⟨hal-00575202⟩

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