Using UV photoionization and delayed near-infrared reexcitation pulses, a novel time-, frequency-, and polarization-resolved pump-repump-probe spectroscopy is conducted in the probing range of 450–2400 nm with improved experimental accuracy. Both the generation process and relaxation dynamics following selective repumping of intermediate species of the solvated electron are investigated and analyzed self-consistently with the help of a kinetic model. New insight in the intermediates of the trapped electron is gained leading to a unique microscopic picture.
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