Experimental Evidence for a Kinetic Transition in Reversible Reactions

We provide a first experimental verification of a theoretical prediction of a kinetic transition in a reversible binding reaction, $\mathrm{AB}\rightleftharpoons A+B$, driven by the difference in effective lifetimes of the bound and the unbound states. We consider the kinetics of excited-state proton transfer to solvent from a photoacid whose conjugate anionic base possesses an extremely short unbound anion lifetime. Its solvent variation relative to the overall dissociation rate coefficient induces a transition in the kinetics, from power law to exponential.