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VOLUME 86, NUMBER 15 P H Y S I C A L R E V I E W L E T T E R S 9 APRIL 2001 Experimental Evidence for a Kinetic Transition in Reversible Reactions
 

Summary: VOLUME 86, NUMBER 15 P H Y S I C A L R E V I E W L E T T E R S 9 APRIL 2001
Experimental Evidence for a Kinetic Transition in Reversible Reactions
Kyril M. Solntsev* and Dan Huppert
School of Chemistry, Raymond and Beverly Sackler Faculty of Exact Sciences, Tel-Aviv University, Tel Aviv 69978, Israel
Noam Agmon
The Fritz Haber Research Center, Department of Physical Chemistry, The Hebrew University, Jerusalem 91904, Israel
(Received 29 June 2000)
We provide a first experimental verification of a theoretical prediction of a kinetic transition in a
reversible binding reaction, AB % A 1 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.
DOI: 10.1103/PhysRevLett.86.3427 PACS numbers: 82.53.k, 78.60.Ps, 82.40.Bj, 82.50.Hp
Physical phenomena normally vary smoothly as a func-
tion of their control parameters. Nevertheless, important
examples of abrupt, discontinuous changes exist and are
the subject of intensive research. In thermodynamic phase
transitions, the many-particle structure of matter changes
discontinuously as a function of thermodynamic parame-

  

Source: Agmon, Noam - Institute of Chemistry, Hebrew University of Jerusalem

 

Collections: Chemistry