Reaction and relaxation processes induced by photoexcitation of an aqueous chloride ion are studied with quantum molecular dynamics simulations. A predominant channel leading to a metastable hydrated electron-chlorine pair is found. By means of theoretical transient and stationary absorption spectra, the solvent reorganization involved in the charge repartitioning is discussed. The dissipation of excess electron kinetic energy by surrounding water molecules plays an essential role in the equilibration of an electron-atom pair. For this intermediate species, two competing reaction pathways are identified. One is the barrier-impeded dissociation yielding a hydrated electron. Shape and height of the free energy barrier determined by quantum umbrella sampling point to a diffusion controlled electron photodetachment. The other channel is the geminate recombination via a nonadiabatic transition for which a self-consistent and fully dynamical treatment of the solvent electronic polarization is found to be important. From the rate constants computed for the individual channels, a kinetic model is derived to explain time-dependent spectral signatures and electron escape yields recently observed in photodetachment experiments on aqueous halides.