The non-Markovian alternative to a conventional rate description of the bie
xcitonic photoinduced processes in solutions was deduced from integral enco
unter theory at sufficiently low concentration of excitations. This is the
unified theory (UT) of photoionization followed by charge separation and re
combination. The UT formalism allowed us to study the initial distribution
of charged products of non-linear (biexcitonic) ionization as well as ion a
ccumulation and recombination after delta-pulse excitation. The Markovian e
quations were obtained from UT as a limiting case and their phenomenologica
l rate constants were given the microscopic definitions, which related them
to the charge transfer rates and encounter diffusion of reactants. In the
case of short lived (singlet) excitations the non-Markovian kinetics was sh
own to be more accurate and detailed than oversimplified Markovian kinetics
. Only for long lived (triplet) excitations the non-Markovian and Markovian
results are qualitatively similar, provided that the properly defined rate
constants are used in the conventional rate equations. (C) 1999 Elsevier S
cience B.V. All rights reserved.