We survey recent experimental and theoretical studies of photodissociation and recombination of dihalide ions in gas-phase clusters and liquid solution. A crucial property of these systems is the flow of excess charge within the solute, which is strongly coupled to the motion of the surrounding molecules. Using a model inspired by the theory of electron-transfer reactions, we have constructed a comprehensive physical picture of the interplay of charge flow and solvent dynamics on multiple, coupled electronic states. The consequences are sometimes surprising: for example, in excited states having antibonding character, the charge moves to the less solvated atom as the solute dissociates, leading to more efficient recombination than in neutral systems. Our analysis also predicts extremely efficient spin-orbit quenching (associated with solvent-induced curve crossings) following UV excitation of I-2(-) clustered with CO2, which has been confirmed by experiment and suggests a revised interpretation of the transient absorption peak seen in pump-probe experiments.