We report a picosecond laser study of the transient absorption of hydrated electrons generated by the 3-5 eV multiphoton ionization of liquid water, The geminate kinetics indicate that e(aq)(-) is produced by at least three different mechanisms over this energy range. Power dependence of the signal amplitude shows a two-photon threshold for 4.0 eV excitation and a three-photon threshold absorption at 3.37 eV, consistent with two- or three-photon excitation of the (A) over tilde(B-1(1)) lowest excited state, For (three-photon) excitation in the range 3.02-3.47 eV very little (less than or equal to 15%) geminate recombination is observed while for the (two-photon) excitation at shorter wavelengths significant recombination (greater than or equal to 55%) is observed. In the region of 3.85-4.54 eV, photon-energy-independent kinetics indicate that e(aq)(-) is produced via two-photon excitation of the (A) over tilde state followed by an ionization process in which the electrons do not obtain any excess kinetic energy, For photon energies in the range of 4.75 - 5.05 eV, the escape fraction increases slightly, consistent with two-photon excitation of higher energy states. Simulation with a diffusion model shows that the electron is ejected at least 25 Angstrom farther into the bulk for the 3.02-3.47 eV photon energies relative to two-photon ionization in the 3.67-5.0 eV range. We conclude that the larger distances result from a (3 + 1)-photon resonance-enhanced multiphoton ionization (REMPT) process, made possible by visible/near-UV absorption of the water excited states. Possible mechanisms of the water ionization are discussed. A new mechanism is proposed to explain the production of solvated electrons from excitation of the (A) over tilde(B-1(1)) state of liquid water, well below the Born-Oppenheimer ionization threshold. On the basis of the gas phase properties of this state, we assume a direct dissociation to give OH radical and H atoms, with the excess energy almost entirely transferred to kinetic energy of the H atoms : H2O* --> OH + H(hot). It is proposed that the hot H atoms immediately react with an adjacent water molecule to form hydronium ion and a solvated electron, in a process analogous to the thermal reaction of H atoms with water at elevated temperatures : H(hot) + H2O --> H3O+ + e(aq)(-).