Ag8 Fluorescence in Argon

The fluorescence of Ag₈ in an argon matrix and in argon droplets is reported. This is the first unambiguous assignment of the fluorescence of a metal cluster larger than the tetramer, indicating that the excited state lifetime is longer than previously thought. It is discussed as a possible result of a matrix cage effect. The excitation spectrum is compared with two-photon-ionization measurements of Ag₈ in helium droplets and to known absorption data. The agreement is excellent. We propose that the excited states relax rapidly through vibrational coupling to a long-lived state, from which the fluorescence occurs.