A new model of solvated-electron systems. Spectral behaviour

Abstract

A new adiabatic model of infinitely dilute solvated-electron systems is described in which the solvent is accorded a dual role suggested by the experimental behaviour of the optical absorption bands attributed to solvated electrons. A small, finite number of solvent molecules and an excess electron, designated as a solvent–anionic-complex, are treated as adiabatic particles; the remaining solvent molecules, comprising a macroscopic solvating system, are treated as averageable particles. As a result, the solvated-electron absorption spectrum is determined by the intrinsic properties of the solvated solvent–anionic-complex.

A basic consequence of the present model is its implication of spectral shape stability of the solvated-electron absorption band when the latter results only from a single band of discrete–continuum transitions of the electron. Under such circumstances, a linear solvated-electron–solvent energy relationship is implied.