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Excitedstate reversible geminate reaction. III. Exact solution for noninteracting partners

Summary: Excited­state reversible geminate reaction. III. Exact solution
for noninteracting partners
Irina V. Gopich
Institute of Chemical Kinetics and Combustion, Russian Academy of Sciences, Novosibirsk 630090, Russia
Noam Agmon
The Fritz Haber Research Center, Department of Physical Chemistry, The Hebrew University,
Jerusalem 91904, Israel
~Received 4 December 1998; accepted 18 February 1999!
An analytic solution is derived for the Green function and survival probability of excited­state
reversible recombination reactions of noninteracting geminate particles in solution, which have
different lifetimes in their bound and unbound states and participate in a competing quenching
reaction. The behavior of the three roots of the cubic polynomial, on which this solution depends,
is investigated in the complex plane. Two kinds of ``complex plane maps'' are identified on which
three types of transitions may occur. One root may vanish, or two roots coincide, or the three real
parts coincide. The first transition leads to a corresponding transition in the long­time asymptotic
behavior, which is derived in the sequel. The quenching and lifetime effects result in nonmonotonic
dependence of the binding probability on the initial separation distance. © 1999 American
Institute of Physics. @S0021­9606~99!50519­9#
A realistic description of geminate excited­state revers­


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


Collections: Chemistry