The dynamics of the photodetachment of an electron from a chloride ion in water induced by excitation of the lowest charge-transfer-to-solvent state is explored by using quantum molecular dynamics simulations. The ejected electron is described in terms of floating Gaussian orbitals, and solvent electronic polarization effects are accounted for in a fully self-consistent way. The simulation results point to a two-step photodissociation mechanism: the formation of a metastable electron - atom pair on a subpicosecond time-scale followed on a picosecond time-scale by the competition between two different reaction channels, (i) a diffusive barrier-impeded dissociation of the pair, yielding a solvated halogen atom and a free electron, and (ii) a non-radiative quantum recombination, eventually leading to the chloride ion in its ground state. The computed transient absorption spectra are compatible with the experimental data either at early times during the formation of the electron - atom pair or at longer times when dissociation - recombination occurs.