Electric field quenching of recombination fluorescence in photoionized nonpolar solutions. I. Free electron quantum yield determination

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Abstract
The field dependence of the relative decrease of fluorescence ΔF/F0 and of the photocurrent, i, is measured for dilute solutions of N,N,N′,N′‐tetramethylparaphenylenediamine (TMPD) in 2,2,4‐trimethylpentane (TMP) and tetramethylsilane (TMSi). In carefully purified and degassed solutions, irradiated by 5.90 eV photons, at 292 K, and E=45 kV cm−1, one obtains: ΔF/F0=3.9×10−2 in TMP and 11.8×10−2 in TMSi. The data are in good agreement with a model based on Onsager theory for electron escape. It is shown how the combined measurement of ΔF/F0 and i permits the determination of the free electron quantum yield at zero field, Φe0. For TMP:Φe0 =1.4×10−2 and for TMSi:Φe0=6.98×10−2. Finally it is shown that the field dependence of Φe, the free electron quantum yield at E, may be calculated from the experimental data.

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