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

Dodin, Dmitry V.; Ivanov, Anatoly I.; Burshtein, Anatoly I.
March 2013
Journal of Chemical Physics;Mar2013, Vol. 138 Issue 12, p124102
Academic Journal
The magnetic field effect on the fluorescence of the photoexcited electron acceptor, 1A*, and the exciplex, 1[D+δA-δ] formed at contact of 1A* with an electron donor 1D, 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+...A-] that proceeds due to hyperfine interaction. We confirm our earlier conclusion (obtained with a rate description of spin conversion) that in the model with a single nucleus spin 1/2 the magnitude of the Magnetic Field Effect (MFE) also vanishes in the opposite limits of low and high dielectric permittivity of the solvent. Moreover, it is shown that MFE being positive at small hyperfine interaction A, first increases with A but approaching the maximum starts to decrease and even changes the sign.


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