Abstract
The compositional behavior of the breadths of absorption bands attributed to solvated electrons in binary mixtures
of mutually nonreacting polar fluids is found to be in quantitative accord with expectations from a two absorber model of solvated electrons. The model basically assumes the following: (1) two kinds of solvated electrons in the mixture of solvents Sj and 8 , that correspond to solvated solvent anions Sj~(s) and SK"(s); (2) a chemical equilibrium between solvated electrons and their solvent progenitors, which is described by Sj"(s) + SK ?=* Sj + Sx~(s); (3) a solvated electron absorption band that is an unresolvable composite of intrinsic absorption bands due to Sj~(s) and Sx'(s), each of which satisfies Beer’s law. To a good approximation, the model implies and applicable systems of polar fluids experimentally satisfy the relationship that 1/W = (xj/Wf) + ( / ), the Ws representing the half-height widths of the solvated electron absorption bands in’the mixtures and in the pure solvents with the x'a corresponding to the relative mole fractions of S.f(s) and SK“(s) in the mixtures. An important implication of the model is that the intrinsic absorption bands due to Sj~(s) ancj SK“(s) are practically coincident, regardless of their relative mole fractions in the mixtures.