Effect of Electric Field Strength on the Free Ion Yields in the X-Radiolysis of Liquids: Influence of Molecular Structure and Temperature

Abstract

The relative increase in the free ion yield with increasing field strength E, expressed as [Formula: see text] is smaller when the following quantities are larger: (1) dielectric constant, (2) temperature, and (3) separation distance between the geminate ion–electron pairs. The field dependence [Formula: see text] equals 9.7/εT2 cm/V at low E, but at higher fields it is affected by the above three factors and by E itself. Results obtained from the liquids propane (123–233 °K), 2-methylpropane (isobutane, 148–294 °K), 2,2-dimethylpropane (neopentane, 295 °K), argon (87 °K), oxygen (87 °K) and argon–oxygen solutions (87 °K) are presented and analyzed according to a theoretical model. Several types of ion–electron separation (y) distribution functions are tested. Within the framework of the model a power function F(> y) = yminy−x with x < 4 provides a good interpretation of the results when [Formula: see text] a Gaussian distribution function provides the best interpretation of the field effects when [Formula: see text] Either the y distribution has a Gaussian core with a more gently sloping tail, or distributions are more Gaussian-like in liquids in which the electron ranges are greater. The electron range in pure argon (b = 1300 Å) is much smaller than had been expected and is only 2.6 times greater than that in liquid methane (b = 500 Å at 120 °K). Phonon emission by 10–0.01 eV electrons in liquid argon may be relatively efficient and might involve transient states of the type [Formula: see text]