Evidence for a second kind of trapped electron in some deuterated aqueous glasses at low temperatures. A pulse radiolysis study

Abstract

Several deuterated aqueous glasses have been pulse-irradiated at 76 K. In addition to the well known visible absorption band of et−, a second intense infrared absorption band, with λmax > 3200 nm, has been found in (a) 50% by volume ethylene glycol, (b) 9.5 M LiCl, and (c) 2.5 and 4 M MgCl2 glasses. Electron scavengers decrease the intensities of both bands, but to different extents. An increase in temperature decreases the intensity of the infrared band, but not that of the visible band. These and other features lead us to conclude that the infrared band is due to shallowly trapped electrons which are distinctly different from trapped electrons which absorb in the visible region.The decay of the infrared band extends over several orders of magnitude in time and, unlike that of the visible band, is independent of wavelength. In the two chloride glasses the decay of the infrared band is accompanied by emission (λmax ≈ 410 nm) and is probably due to a spur reaction between an electron and hydroxyl radical to form excited hydroxide ion. No emission is found in the ethylene glycol glass, but growth of the visible band matches the decay of the infrared band in this case.By comparing the amount of Ag0 produced in an ethylene glycol glass containing Ag+ with the decrease in intensity of the infrared and visible bands, we obtain ε1400 = (5.7 ± 0.8) × 103 M−1 cm−1. From the shape of the infrared band, which is Lorentzian on the high energy side, we estimate λmax ≈ 3600 nm and εmax ≈ 4.9 × 104 M−1 cm−1.