Abstract
External magnetic field effects on the recombination fluorescence (MARY effect) in the photoionization reaction of N, N, N′, N′‐Tetramethyl‐p‐phenylenediamine (TMPPD) in water and DMSO/water mixture are studied. Relatively large magnetic field effects (MFE), ∼ 2–4%, on the fluorescence yield are observed in the extremely polar water solvent under magnetic fields as small as 3 mT. Such MFE is hardly expected in water due to instability and very fast escape of the solvated electron from the solvent cage. Enhancement in the signal‐to‐noise ratio and superior time resolution characterizing the technique of field modulation allowed the detection of a very short lived radical ion pair (about 1 ns). The observed MARY spectra illustrate that the singlet radical ion pair is more reactive than the triplet one.
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