Electron and cation transport in fluid dimethyl ether: effects of density and temperature

The effect of molecular electric dipole moment D on charge transport in fluids was examined by measurement of electron and ion mobilities in dimethyl ether (D = 1.3 D) and comparing them with the behavior in hydrocarbons. The fluid density was varied continuously from that of the normal vapor to that of the normal liquid, passing through the critical region. The density normalized mobility nμe of electrons in dimethyl ether vapor at low densities is 30-fold smaller than that in propane, although for the cations nμ+ in the ether is only 1.4-fold smaller than that in the alkane. The permanent dipole moment of the ether dominates the scattering of low energy electrons but not that of cations. The electron momentum transfer cross section is roughly 33% larger than that predicted by the Altshuler point dipole model, and has a minimum at ~0.12 eV. The energy gained from the electric field is removed mainly through inelastic collisions, even in the thermal energy range.Molecular clustering decreases both electron and ion mobilities, but the effect on the former is much larger due to the greater change in reduced mass. The extent of electron quasilocalization in the dense vapor of dimethyl ether is four times greater than that in nonpolar hydrocarbons. Electrons form relatively stable localized states in the liquid at n/ne > 2.0. Ion mobility undergoes a transition from "density control" to "viscosity control" with increasing density in the low density liquid. Viscosity control is operative at n/ne > 2.4.