  The excess electron in liquid ammonia ("ammoniated electron") is commonly
viewed as a cavity electron in which the s-type wave function fills the
interstitial void between 6-9 ammonia molecules. Here we examine an alternative
model in which the ammoniated electron is regarded as a solvent stabilized
multimer radical anion, as was originally suggested by Symons [Chem. Soc. Rev.
1976, 5, 337]. In this model, most of the excess electron density resides in
the frontier orbitals of N atoms in the ammonia molecules forming the solvation
cavity; a fraction of this spin density is transferred to the molecules in the
second solvation shell. The cavity is formed due to the repulsion between
negatively charged solvent molecules. Using density functional theory
calculations for small ammonia cluster anions in the gas phase, it is
demonstrated that such core anions would semi-quantitatively account for the
observed pattern of Knight shifts for 1-H and 14-N nuclei observed by NMR
spectroscopy and the downshifted stretching and bending modes observed by
infrared spectroscopy. It is speculated that the excess electrons in other
aprotic solvents (but not in water and alcohols) might be, in this respect,
analogous to the ammoniated electron, with substantial transfer of the spin
density into the frontier N and C orbitals of methyl, amino, and amide groups
forming the solvation cavity.
