Transfer reactions of Rydberg electrons in condensed media .2. Manifestation of femtosecond processes in the quasi-steady-state kinetics of delayed fluorescence of aromatic solutes in toluene matrix at 77 K

A kinetic scheme is presented to describe the results of the previous experimental study on the mechanism of delayed fluorescence of aromatic solutes: naphthalene-D-8, chrysene-D-12 (A), and biphenyl (B) in toluene matrix at 77 K, fluorescence being induced via photoexcitation of the solutes from their phosphorescent states T-1 to higher excited states T*. It was shown that rate constants for Rydberg electron transfer from the primary radical anions A(1)(radical anion) to various secondary centers, A(2)(S-0), A(2)(T-1), and B(S-0), are identical (S-0 denotes the singlet ground state of a solute). This invariance is due to the fact that electrons are captured within femtoseconds onto Rydberg p, d, and f orbitals of the atoms that carry excess positive charges (delta+), in polarized solute molecules possessing identical functional groups C-delta+-H and C-delta+-D (or C-H-delta+ and C-D-delta+).