Conduction state energy of excess electrons in condensed media. Liquid methane, ethane, and argon and glassy matrices

Abstract

27) One of the reviewers pointed out that the local electric field produced by a point charge Immersed in a continuous dielectric (without cavities) is simply q/ 2. In this Instance, the dipole screening function would be unity. The argument proceeds as follows. The local electric field is given by the field due to the point charge, namely, q/t2, plus the sum of the fields due to microscopic electric dipoles induced in the dielectric. Inasmuch as all the polarization In the dielectric Is directed radially toward the charge, Its contribution to the local field cancels out, making the local electric field simply q/t2. This argument can In fact be verified by replacing the fluid radial distribution function in eq 11 of ref 4 by unity and performing the Indicated integration. A fluid characterized by a radial distribution function, which is unity everywhere, is a fluid in which the molecules may overlap. The physical Impossibility of molecules overlapping is In some sense taken into account in the cavity model used in this paper. That is to say, the cavity boundary surrounding the Induced multipoles prevents the uniform dielectric representing the remaining molecules from approaching the multipoles too closely. To this extent, the repulsive aspect of the intermolecular force has been taken Into account.Conduction State Energy of Excess Electrons in Condensed Media.

Photostimulated electron detrapping and the two-state model for electron transport in nonpolar liquids

“…5(c)). The increase in V 0 , as shown elsewhere, 86 can be rationalized using the model of Springett, Jortner, and Rice 46 in its formulation by Kevan et al 87 This is illustrated in Fig. 5(c) using the experimental data for n-hexane 86 and calculated V 0 energies for methylcyclohexane.…”

“…Also shown are the V 0 energies for n-hexane (empty triangles; to the left) and theoretical estimates of this energy using the approach of ref. 87. Molecular polarizability of 13.1 Å 3 and Wigner-Seitz radius of 2.235 Å for methylcyclohexane were assumed in the calculation.…”

Theoretical models for solvated electrons

“…However, now a number of V0 values have been measured using a photoionization threshold method for a variety of alkanes. [43][44][45] These values can be used directly in the semicontinuum model when it is properly modified for nonpolar systems. The mobilities of excess or quasi-free electrons in the delocalized conduction state also provide relevant dynamic information about the electron.…”

Determination of energies of quasifree electron state V0 in organic solids from electron transmission spectra

“…The energies of quasifree electron state V0 have been reported for several liquid hydrocarbons.1'5 However, attempts to measure V0 directly in polar or nonpolar glassy matrices have failed. 5 The V0 values in glassy matrices have been estimated by an indirect method using eq l,5-7 4 4 = /g + 7^+ v0 (l) where I\ and 7S are the ionization potential of an impurity molecule A in a liquid and solid solution, respectively, 7g is the gas phase ionization potential of A, 7*" is the polarization energy of the medium by the positive ion A+, and V0 is the energy of quasifree electron state.…”