title: Experimental evidence for a kinetic transition in reversible reactions.
abstract: We provide a first experimental verification of a theoretical prediction of a kinetic transition in a reversible binding reaction, AB right harpoon over left harpoon 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.
authors.affiliation: School of Chemistry, Raymond and Beverly Sackler Faculty of Exact Sciences, Tel-Aviv University, Tel Aviv 69978, Israel.
authors.forename: K M
authors.initials: KM
authors.lastname: Solntsev
authors.forename: D
authors.initials: D
authors.lastname: Huppert
authors.forename: N
authors.initials: N
authors.lastname: Agmon