Uniform theory of electron kinetics in nonpolar liquids

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Abstract
Application of the Smoluchowski–Debye equation results in a uniform treatment of the kinetics of either of the bulk reactions e− +M+→M or e−+A→A−, and the corresponding photoionization reaction, either M⇄hνM++e− or A−⇄hνA+e−. For simplicity of terminology, the bulk reactions are referred to as class I and the photoionizations as class II. Included in the theory are the following effects: (1) solvent screening of the interaction potential between e− and either of the acceptors M+ or A, (2) spatial variation of electron transport coefficients (mobility and diffusion tensor) due to the internal electric field associated with the interaction potential, (3) electron tunneling, and (4) chemical activation processes. By use of Green’s function methods, we arrive at the result n1(r)exp[−ψ (r)]=NsP (r), where n1(r) is the pair density at a relative separation r in a reaction of class I, and P (r) is the escape probability for a pair initially at a separation r in the corresponding reaction of class II. The quantity Ns is the electron concentration in the class I reaction (Ns=NM+ or NA).