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26 March 1999 Z .Chemical Physics Letters 302 1999 399404

Summary: 26 March 1999
Z .Chemical Physics Letters 302 1999 399­404
Kinetic transition in excited-state reversible reactions
Noam Agmon )
, Irina V. Gopich 1
The Fritz Haber Research Center, Department of Physical Chemistry, The Hebrew UniÕersity, Jerusalem 91904, Israel
Received 10 November 1998; in final form 1 February 1999
We demonstrate that reversible reactions occurring in the excited electronic state undergo a `kinetic transition' as a
function of the difference in excited-state decay rates. This conclusion follows from a remarkably accurate approximate
solution obtained for the kinetics of diffusion-influenced reversible geminate dissociation reactions in solution, which
becomes exact at long times. q 1999 Elsevier Science B.V. All rights reserved.
1. Introduction
Solution-phase chemistry provides several impor-
tant examples of reversible diffusion-influenced reac-
tions in the excited electronic state. An interesting
case is presented by excited-state proton transfer to
solvent from excited hydroxyarenes, a prototype acid
w xdissociation reaction 1­6 . The reaction is schemati-
cally depicted by


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


Collections: Chemistry