Ground-state properties and optical excitations of a solvated electron in molten alkali halides

Properties of solvated electrons at high dilution in four molten alkali halides are investigated theoretically. A self-consistent evaluation of the bound ground state of the electron and of the surrounding liquid structure, already developed in a previous paper, is compared with the results of NMR hyperfine shifts and magnetic susceptibility measurements. The absorption bands associated with Franck-Condon 1s→2p and 1s→3p transitions are calculated and compared with the available data of optical absorption, with special emphasis on the detailed analysis by Yuh and Nachtrieb for molten CsCl. An instability of the excited states against ionic relaxation and the origin of a finite lifetime for the ground state are also discussed. Finally, the perturbation induced by the solvated electron in the fundamental absorption of the molten salt is estimated. (author)