PULSE-RADIOLYSIS ANALYSIS OF SPECTRAL AND KINETICS PROPERTIES OF THE SOLVATED ELECTRON IN LIQUID HEXANE-1,2,6-TRIOL

The optical absorption spectrum of the solvated electron (e(s)(-)) in liquid hexane-1,2,6-triol has been measured by nanosecond pulse radiol ysis at different temperatures (10-40 degrees C) to investigate the in fluence of high solvent viscosity values on the spectral and kinetic p roperties of e(s)(-). The wavelength at the absorption maximum, lambda (max), is equal to 560 nm, and its variation with temperature, if it e xists in the considered zone, is less than the experimental error. At 20 degrees C and 150 ns, the value of the product G is an element of(m ax) Of the yield of e(s)(-) and the molar extinction coefficient at la mbda(max) is 2.55 x 10(4) molecule/(M cm 100 eV). In the context of th is work, we have compared results obtained with both a linear accelera tor and a Febetron, a comparison that has allowed us to evaluate the i nfluence of variations of the dose per pulse and to extend measurement s to short times. In the case of experiments performed with the linear accelerator, e(s)(-) is found to decay at all wavelengths by a first- order reaction (or by a pseudo-first-order reaction) with an activatio n energy of similar to 45 kJ mol(-1). By contrast, kinetic curves obta ined with the Febetron seem to show a competition in which a second-or der law is followed at short