Abstract
We have produced solvated electrons (esolv−) in ethylene glycol (EG) by irradiation of a 248 nm laser pulse in the charge-transfer-to-solvent (CTTS) band of I− (resonant photodetachment). We report on the optical absorption spectra of esolv− as a function of temperature. A red-shift of the position of the absorption maximum, Δℏωmax≈−0.4 eV, corresponding to d(ℏωmax)/dT=−(2.49±0.07)×10−3 eV K−1 in the temperature range 296⩽T⩽453 K is reported. The observed absorbance of esolv− at ℏωmax increases by a factor of about 60 when the temperature is increased from 296 to 453 K. This effect can be explained only partially by the favorable red-shift of the CTTS spectrum of I− with respect to the laser wavelength by increasing the temperature. The self diffusion coefficient in EG is by a factor of 25 lower than in water at 298 K and increases strongly with temperature. It is concluded that a reaction step with a diffusion controlled escape probability for the electron determines the yield of esolv−. The results are, therefore, analyzed according to a simple kinetic model proposed by Staib and Borgis [J. Chem. Phys. 104, 9027 (1996)].
Published Version
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