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.