Two types of localized excess electrons in crystalline D2O ice

Abstract

In a pulse radiolysis study of crystalline D2O ice, an intense infrared absorption band with λmax > 2350 nm has been found at low temperatures, in addition to the well-known visible absorption band of the trapped electron. The infrared band is also attributed to trapped electrons, partly because of its similarity to the electron absorption band found recently in some D2O glasses at low temperatures. The effects of temperature, dose per pulse, accumulated dose, and added NH4F, HF, and ND3 on the yields and decay kinetics of both bands have been investigated. It is concluded that the electron trap giving rise to the visible band is a vacancy which at low temperatures is radiation-produced by a two-step spur process. At temperatures close to the melting point the vacancy-trap probably exists before the radiation pulse at equilibrium concentration. The electron trap which gives rise to the infrared band is thought to be a cavity that occurs naturally in the perfect lattice. For previously unirradiated samples the infrared band decays by a second order process which is remarkably fast [Formula: see text] The decay reaction is probably neutralization by D2O+. Doping with NH4F increases the yield of the infrared absorption and greatly decreases its decay rate. The total yield of localized electrons in irradiated crystalline D2O is higher than has been generally recognized.