Hyperfine interaction mechanism of magnetic field effects in sequential fluorophore and exciplex fluorescence.

The magnetic field effect on the fluorescence of the photoexcited electron acceptor, (1)A∗, and the exciplex, (1)[D(+δ)A(-δ)] formed at contact of (1)A∗ with an electron donor (1)D, is theoretically explored in the framework of Integral Encounter Theory. It is assumed that the excited fluorophore is equilibrated with the exciplex that reversibly dissociates into the radical-ion pair. The magnetic field sensitive stage is the spin conversion in the resulting geminate radical-ion pair, (1, 3)[D(+).

Magnetic field effect in fluorescence of excited fluorophore equilibrated with exciplex that reversibly dissociates into radical-ion pair undergoing the spin conversion.

The fluorescence of the photoexcited electron acceptor, (1)A∗, and the exciplex, (1)[D(+δ)A(-δ)] formed at contact of (1)A∗ with an electron donor (1)D, is known to be very sensitive to a magnetic field, assisting the spin conversion in the resulting geminate radical ion pair (RIP), (1, 3)[D(+)...

Noncontact bimolecular photoionization followed by radical-ions separation and their geminate recombination assisted by coherent HFI induced spin-conversion.

The Hamiltonian description of the spin-conversion induced by a hyperfine interaction (HFI) in photogenerated radical-ion pairs is substituted for the rate (incoherent) description of the same conversion provided by the widely used earlier elementary spin model. The quantum yields of the free ions as well as the singlet and triplet products of geminate recombination are calculated using distant dependent ionization and recombination rates, instead of their contact analogs. Invoking the simplest models of these rates, we demonstrate with the example of a spin-less system that the diffusional acceleration of radical-ion pair recombination at lower viscosity gives way to its diffusional deceleration (Angulo effect), accomplished with a kinetic plateau inherent with the primitive exponential model.