Photoelectron emission (PEE) by potassium (0.002–3 mole liter−1) and sodium (0.013–0.21 and 7.2 mole liter−1) in liquid ammonia at −60°C was studied from 1.55 to 5.4 eV. The PEE spectrum is composed of the previously reported band with its maximum about 3.2 eV and a new band peaking about 4.6 eV. The highly asymmetric low‐energy band is assigned to PEE by solvated electrons. Its interpretation by a recent model for PEE by solutions results in a linear dependence of the range of quasifree electrons in solution on photon energy. The quantum yield appears to be proportional to the square root of the analytical metal concentration up to 0.1 mole liter−1. The 4.6 eV symmetric PEE band is interpreted as the result of bound‐bound transitions (similar to β band for F centers) followed by autoionization. Experimental methods are outlined, and their details are available in an unpublished report.

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N. R. Kestner and J. Jortner (unpublished); manuscript kindly supplied by Authors.
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Absorption spectra in the high‐energy tail, which are available in Eding’s dissertation, are not sufficiently accurate for our purpose; H. J. Eding, “Absorption Spectra of Metal‐Ammonia and Metal‐Methylamine Solutions,” Ph.D. dissertation, Stanford University, Stanford, Ca 1952.
16.
For temperature and concentration effects, see J. Hurley, T. R. Tuttle, and S. Golden, Ref. 5, p. 503.
17.
W. E. Mueller and J. C. Thompson, Ref. 5, p. 293.
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Partial substitution of liquid ammonia by tetrahydrofuran had two rather minor effects: (a) a red shift in agreement with similar observations on the absorption spectrum of solvated electrons in mixed solvents [see
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(b) an increase in quantum yields (10% for low‐energy band; 25% for high‐energy band) resulting from a variation in the probability of escape of generated quasifree electrons and/or from a shift in chemical equilibria in solution and their effect on the probability of geminate recombination between parent emitter and quasifree electrons in solutions.8
22.
E. J. Hart, Ref. 5, p. 413.
23.
B. Fowler, Physics of Color Centers, edited by B. Fowler (Academic, New York, 1968), p. 93;
F. Lüty, ibid., p. 196.
24.
The authors of Ref. 18 claimed that this band was not observed with improved technique, but their accompanying figure does show the band, as in the earlier Ref. 17.
25.
J. Jortner, Ref. 5, pp. 297 and 299.
26.
An alternate interpretation can be offered: The high‐energy PEE band results from a nonmonotonic increase of the range of quasifree electrons in solution with kinetic energy. However, no such behavior has been reported for nonpolar liquids [
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