Electronic (one-photon) photodepletion spectra were recorded for gold cluster anions complexed with one xenon atom over the photon energy range 2.1-3.4 eV. Clusters were generated by pulsed laser vaporization and probed under collisionless molecular beam conditions. The spectra obtained are highly structured with the narrowest features-assigned to individual electronic transitions-having bandwidths of less than 40 meV. Time-dependent density functional theory predictions of optically allowed transitions for the most stable-planar-isomers of the corresponding bare metal cluster anions are generally consistent with the experimental observation. (C) 2004 American Institute of Physics.