Novel precursors of solvated electrons in water: evidence for a charge transfer process.

Femtosecond midinfrared spectroscopy of water (heavy water) after two photon excitation at 9 eV provides clear evidence for two short-lived precursors of the hydrated electron preceding the well-known "wet electron." The measured first intermediate with peak absorption at 2.9 (4.1) microm is proposed to represent an O(H, D):e(-) complex. The subsequent solvation proceeds via e(-):[(H, D)2O](n) complexes at approximately 1.6 (2.0) microm in the electronic ground state, involving an increasing number of water molecules during the first 200 fs and followed by the wet electron.