Improved experimental methods for photoelectron emission (PEE) spectroscopy of solutions were developed and applied to aqueous solutions of K4Fe(CN)6 and similar emitters. Aspects covered for K4Fe(CN)6: back scattering of electrons in water vapor; lack of detectable Schottky effect; determination of a red shift of the PEE spectrum at constant current upon temperature increase (≈ − 5 × 10−4 eV per degree); variation of quantum yield (≈ 2 × 10−9 to ≈ 2 × 10−5 collected electron per incident photon) with photon energy for concentrations from 0.005 to 0.1 mole liter−1; dependence of molar quantum yield on emitter concentration. PEE spectra are also given for 0.1M aqueous solutions of Na3[Fe(CN)5H2O], Na3[Fe(CN)5NH3], K4Mn(CN)6, K4Ru(CN)6, K4Mo(CN)8, K4W(CN)8.
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Nemec et al. (1972) studied this question.
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