Mobilities and Ranges of Electrons in Liquids: Effect of Molecular Structure in C5–C12 Alkanes

Abstract

X-radiolysis free ion yields and electron mobilities were measured in a series of branched chain hydrocarbons at several temperatures. The numbers listed after the following compounds are the temperature (K), Gfi, most probable penetration range of the secondary electrons (Å) and thermal electron mobility (cm2/V s): 2,2-dimethylpropane (neopentane), 294, 1.09, 213, 50; 2,2,3,3-tetramethylbutane, 379, 0.80, 130, –; 2,2,4,4-tetramethylpentane, 295, 0.83, 158, 24; 2,2,5,5-tetramethylhexane, 293, 0.67, 138, 12; 2,2,6,6-tetramethylheptane, 293, 0.47, 113, –; 2,2,7,7-tetramethyloctane, 383, 0.58, 100, –; 2,2,3,3-tetramethylpentane, 295, 0.42, 102, 5.2; cyclohexane, 294, 0.16, 67, 0.45. The difference between the activation energies of the reactions[Formula: see text]and[Formula: see text]is (E15–E14) ≈ (2 to 3)RT for twenty two different hydrocarbons, including olefins and benzene. The rate of energy loss by epithermal electrons in liquid hydrocarbons increases with increasing anisotropy of polarizability of the molecules or groups; the range of the electron interaction in a given molecule appears to be about two C—C bonds in series (groups up to neopentyl in size). There is a correlation between the mobilities of thermal electrons in liquids and the penetration ranges of the secondary electrons in the liquids. The electron mobility in a liquid alkane appears to be limited by inelastic scattering. The inelastic scattering cross sections for both thermal (< 0.1 eV) and epithermal (~ 1 eV) electrons in liquid alkanes are affected in similar ways by the anisotropy of polarizability of the molecules. In both instances the scattering apparently involves rotational (librational) excitation of the medium.