Theoretical studies on the composition of the absorption spectrum of the solvated electron

Investigations on the optical spectrum of electrons in polar fluids were extended to the study of the influence of cavity distortions, the higher excited states, and the role of the two electron cavity species. The higher excited states with l = 1 were studied by simple models using numerical solutions of the differential equations and by solutions of the Copeland--Kestner--Jortner model (CKJ). In ammonia the second excited state is predicted to lie about 0.44 to 0.52 eV above the first, depending on the technique used. Most cavity distortions do not split the l = 1 components. Those that do, yield only a small difference in energy of the levels. Improved calculations of the two electron cavity species are presented. That species is larger than the one electron cavity. Calculations using a screened interelectronic interaction predict a stable two electron species which becomes marginally stable when solvent effects are included. Thus none of these studies can explain the observed spectrum. A reinvestigation of the long-range electron--solvent interaction is needed. Preliminary results of such studies, using the recent work of Dogonadze et al. are included. Agreement with experimental results is greatly improved